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• Atomic, Molecular and Optical Physics  (654)
• Physical Chemistry  (345)
• 1970-1974  (697)
• 1965-1969  (302)
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• 1
Electronic Resource
New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The oxidation of inositol by quinquevalent vandadium in acid medium is a first-order reaction both in vanadium (V) and inositol. The stoichiometry of the reaction is consistent with the use of two equivalents of vanadium (V) per mole of inositol with the formation of one mole of inosose. The reaction is catalyzed both by sulfuric and perchloric acid, but the rate is faster in sulfuric acid than in perchloric acid. In 1M-6M perchloric acid solutions the reaction has shown a variable order in H+, but in solutions of 2M-5M sulfuric and perchloric acid of constant ionic strength, the rate has a linear dependence on [H+]2. There is also a linear correlation between the rate and bisulfate ions in sulfuric acid at constant hydrogen ion concentration. The energy of activation is found to be 19 kcal/mole and a negative entropy value of - 14 e.u. A suitable mechanism, consistent with the kinetics in 2M-5M acid solutions, is suggested and the values of various rate constants are evaluated.
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• 2
Electronic Resource
New York, NY : Wiley-Blackwell
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 Mg2+ and Eriochrome-Black-T (EBT) has been investigated in the pH range between 7.05 and 9.0, in the presence of 12% ethanol. The reaction is found to consist of two parallel paths, one involving the tervalent unprotonated ligand, and one its monoprotonated form. The rate constant for the unprotonated ligand has a “normal” value, whereas that for the protonated form is much lower. The numerical value of the rate constant for the unprotonated ligand obtained from results at a magnesium concentration of 10-3M and a pH up to 9.0 is, however, inconsistent with that obtained from results at [Mg2+] = (1 to 4) × 10-3M and pH up to 8.1. This can be explained, at least partially, if we assume the intermediate MgHD to lose its proton not only to H2O, but also to other bases present in the solution.
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• 3
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The kinetics of the alkaline hydrolysis of five diol monoesters and related esters in aqueous DMSO, aqueous acetone, and aqueous ethanol are reported. A novel solvent dependency of the reactivity pattern of the various esters is noticed. The results are explained on the basis of an internal stabilization of the transition state and the influences of the various solvent systems on such transition states. It is suggested that such dipolar aprotic-protic solvent influences on reaction rates can be used as a criterion in the assessment of anchimeric assistance in such reactions.
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• 4
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The process of acetal hydrolysis is analyzed in terms of the competing steps of proton transfer and heavy atom reorganization. The results of this analysis are portrayed in a series of three-dimensional reaction coordinate diagrams. The observed pathway of hydrolysis (A-1, general acid catalyzed, or spontaneous) is shown to depend on the energy of the various possible intermediates in these reactions.
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• 5
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The preparation and characterization of the iron(II) complex of the hexadentate Schiff base ligand NN‴-bis-[α-(2-pyridyl)benzylidene]triethylenetetramine are reported. Kinetic patterns and rate constants for aquation of this complex, and for its reactions with hydroxide, cyanide, and peroxodisulphate have been determined. Activation parameters for the reaction with cyanide, in aqueous solution, are ΔH
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• 6
Electronic Resource
New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Methods are discussed for the production and detection of the hydroperoxyl radical for use in gas phase kinetic studies. Rate constants for gas phase reactions of the hydroperoxyl radical with itself, H2, H2O, CO, NO, SO2, O3, C2H6, C3H8, i-and n-C4H10, C2H4, i-C4H8, HCHO, C2H5CHO, n-C3H7CHO, Br, O, OH, and H are critically evaluated. Recommended or estimated rate constant expressions with associated error limits are given applicable over specified temperature ranges (normally 300-1000°K). The reactivity of HO2 compared with OH, O, H, F, Cl, Br, CH3, and CH3O is presented in tabular form and the implications for atmospheric chemistry are discussed.
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• 7
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The pyrolysis of C6F5I has been studied by the toluene carrier method over the temperature range of 900-978°K with contact times of 0.4-2.0 seconds and total pressures of 11.2-19.5 torr. Percent decomposition ranged from 8.6 to 97.7%. With toluene-to-C6F5I molar ratios of greater than 150, 85-100% of the C6F5 released abstracts a hydrogen atom from toluene to produce C6F5H. No significant quantities of I2 were observed and the only major gaseous product was HI. Within the limits of the experimental method the decomposition of C6F5I was first order and homogeneous.Least squares analysis of log k1 and 103/T(C6F5I → C6F5 + I) values gives \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}\,k_1 ({\rm s}^{- 1}) = 15.9 - 69,200/4.576T$$\end{document} while a weighted line of best fit yields. \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}\,k_1 ({\rm s}^{- 1}) = 15.4 - 67,000/4.576T$$\end{document} Based on this latter equation D[C6F5—I] at 298°K is estimated as 66.2 kcal/mole.
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• 8
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The kinetics of the gamma-radiation-induced free radical chain reaction in solutions of C2Cl3F in cyclohexane (RH) was investigated over a temperature range of 87.5-200°C. The following rate constants and rate constant ratios were determined for the reactions: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2a)}} & {{\rm R} + {\rm C}_{\rm 2} {\rm Cl}_{\rm 3} {\rm F} \to {\rm RCClFCCl}_{\rm 2}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(2{\rm b})} & \to \\ \end{array}{\rm RCCl}_{\rm 2} {\rm CClF}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c}{{\rm (3a)}} & {{\rm RCClFCCl}_{\rm 2} \to {\rm RCF}}\\ \end{array}{\raise1pt\hbox{\Relbar \kern-4pt{\Relbar}}}{\rm CCl}_{\rm 2} + {\rm Cl}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (4a)}} & {{\rm RCClFCCl}_{\rm 2} + {\rm RH} \to {\rm RCClFCCl}_{\rm 2} {\rm H} + {\rm R}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{2a} ({\rm mole}^{{\rm - 1}} 1.\,{\rm sec}^{{\rm - 1}}) = (8.64 \pm 0.35) - (6.38 \pm 0.41)/\theta ^1$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{{\rm 2b}} /k_{{\rm 2a}} = (- 0.03 \pm 0.15) - (2.39 \pm 0.28)/\theta$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm (}k_{3{\rm a}} /k_{4{\rm a}})({\rm mole}\,1.^{{\rm - 1}}) = (6.17 \pm 0.10) - (10.14 \pm 0.18)/\theta$$\end{document} In competitive experiments in ternary solutions of C2Cl4 and C2Cl3F in cyclohexane the rate constant ratio k2c/k2a was determined \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2c)}} & {{\rm R} + {\rm C}_{\rm 2} {\rm Cl}_{\rm 4} \to {\rm RC}_{\rm 2} {\rm Cl}_{\rm 4}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{{\rm 2c}} /k_{{\rm 2a}} = (0.13 \pm 0.06) - (1.20 \pm 0.12)/\theta$$\end{document} By comparing with previous data for the addition of cyclohexyl radicals to other chloroethylenes it is shown that in certain cases the trends in activation energies for cyclohexyl radical addition can be correlated with the C—Cl bond dissociation energies in the adduct radicals.
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• 9
Electronic Resource
New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
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• 10
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Different possible mechanisms for the gas phase reaction of formation of bromine chloride from bromine and chlorine are discussed. The rate of the reaction has been deduced from photometric measurements in conventional static reactors of surface-to-volume ratio ranging between 0.6 and 3 cm-1, at temperatures between 51 and 113°C. Experimental data show that (1) the observed reaction is predominantly heterogeneous, and (2) the homogeneous reaction must proceed by an atomic chain mechanism initiated by Br atoms.
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• 11
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New York, NY : Wiley-Blackwell
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.
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• 12
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The thermal decomposition of ethylallylether (EAE) has been studied in the gas phase over the temperature range of 560-648°K. Propylene and acetaldehyde are the only reaction products observed. The reaction is apparently homogeneous in nature and independent of the pressure of EAE and of added foreign gases. The experimetally determined first-order rate constants, using the internal standard technique, fit the Arrhenius relationship log k(s-1) = 11.84 ± 0.29 - (43.57 ± 0.77 kcal/mole)/2.303RT. Independently the same rate constants are obtained, based on the amounts of products formed. The observed activation parameters are in general agreement with expectations based on the concept of a 6-center 1,5-H-shift retro-“ene” reaction mechanism, and they agree with previous results obtained for the similar reactions involving alkylallylamines and olefins.
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• 13
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: A competitive method involving the direct measurement of radical concentrations by EPR spectroscopy has been used to show that in solution at 25°C the rate constants for the bimolecular self-reactions of ethyl, isopropyl, tert-butyl, cyclopentyl, and trichloromethyl are all approximately equal, as had been indicated previously by direct measurement of the rate constants for decay of these radicals.
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• 14
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Nucleophilic substitution reactions in the alkyl halides, RX + Y- → RY + X-, proceeding in polar media are considered on the basis of the theory presented in Part A. It is shown that the solvent reorganization energy is the main part of the activation energy for this processes. According to calculations performed, the values of the solvent reorganization energy equal ∼2.5-3 eV for H2O and ∼ 1.8-2.3 eV for acetone. From experimental data on the kinetic isotope effect, an estimate for the splitting of nonadiabatic terms and for the slope of the potential curve v′ of the intermolecular interaction between halide ion and methyl halide near transition configuration is made. Further, the parameter v′ is used for calculating the activation entropy of substitution reactions in the methyl halides. Theoretical activation energies and activation entropies agree with experimental values. In the framework of theory presented an interpretation of change of Ea and the preexponential factor with the type of alkyl halide is given.
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• 15
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Measurements of rates of oxygen absorption and steady-state peroxy radical concentrations for the autoxidation of tetralin in the presence of tert-butyl hydroperoxide have shown that the rate constant for reaction of the tert-butylperoxy radical with tetralin at 60°C is approximately 11.0 M-1 s-1. This rate constant is about a factor of 4 larger than the value recently reported by Niki, Okayasu, and Kamiya for this reaction.The present work emphasizes that great care should be taken when the hydroperoxide method is used to estimate cross-propagation rate constants for a substrate as reactive as tetralin at a temperature as high as 60°C.
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• 16
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The addition of propene to cyclohexa-1,3-diene has been studied between 512 and 638°K at pressures between 70 and 640 torr. The products are endo- and exo-5-methylbicyclo [2.2.2] oct-2-ene, and their formations are second order. The rate constants (in 1./mole-sec) are given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k_{{\rm endo}} = - (26070 \pm 80)/4.576T + (5.74 \pm 0.03)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k_{{\rm exo}} = - (30090 \pm 80)/4.576T + (6.66 \pm 0.03)$$\end{document} The results are discussed in terms of a biradical mechanism.
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• 17
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The kinetics of the decay of hydroxyl radicals in the presence of excess acetylene were studied at pressures in the vicinity of 1 torr and at ambient temperature in a tubular discharge-flow reactor. Hydroxyl radicals were produced by the reaction of atomic hydrogen with nitrogen dioxide, H + NO2 → OH + NO. The concentration of hydroxyl was followed by line absorption photometry at 308.939 nm and 308.328 nm. Second-order rate coeffcients were determined in two sets of experiments. The initial concentration ratio [C2H2]0/[OH]0 was in the range of 2.3 to 13.2 in the first set, and 14 to 125 (owing to greater hydroxyl detection sensitivity) in the second set. Values of the second-order rate coefficient obtained were nk5 = (2.9 ± 0.3) × 10-13 cm3/molec-sec in the first set, and nk5 = (2.1 ± 0.6) × 10-13 cm3/molec-sec in the second set, where n is the stoichiometric coefficient of OH. A value of the bimolecular rate constant k5 = (2.0 ± 0.6) × 10-13 cm/molec-sec is consistent with both sets of data, as well as an earlier determination.
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• 18
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The rate of vibrational relaxation of HF(v = 1) by F atoms has been calculated using quasi-classical trajectory techniques. An attempt has been made to account for the effects of multiple potential energy surfaces on the vibrational relaxation efficiency within the electronically adiabatic assumption. Toward this end two potential energy surfaces were investigated. The LEPS equation was used to construct a reactive surface for F + HF′ → FH + F′ having a reaction barrier height of 5.4 kcal/mole, which is in agreement with a bond energy-bond order prediction. A nonreactive interaction potential consisting of atom-atom Morse functions was calibrated to Noble and Kortzeborn's [J. Chem. Phys. 52, 5375 (1970)] LCAO-MO-SCF results for FHF(2II). The results are in qualitative agreement with experiment. However, the nonreactive surface appears to be too repulsive, and consequently, the contribution of collisions on the nonreactive surface to the total vibrational relaxation rate coefficient are overestimated.
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• 19
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The electron transfer reactions of the superoxide ion with benzoquinone, trimethylbenzoquinone, and menadione in dimethylformamide were studied. A procedure of the determination of the relative rate constants of these reactions was developed; the reaction of O—2 with butyl bromide was chosen as a standard one. The relative rate constants measured at 20,°, 35°, and 50°C were slightly dependent on the quinone structure.The relationship between the free energy ΔF*of the electron transfer reactions and the standard free energy ΔFo was discussed. This relationship is proposed as ΔF* = αΔFo + β, where the proportionality coefficient α is equal to 0.04-0.11 for exothermal reactions and to 0.90-0.96 for endothermal reactions.
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• 20
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
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• 21
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The reactions \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(1)} {{\rm O + HNO}_3 \to {\rm products}}\\ {(2)} {{\rm H + HNO}_{\rm 3} \to {\rm products}} \end{array}$$\end{document} have been studied in a discharge-flow system. Kinetic studies were made using resonance fluorescence for the measurement of atom concentrations. Based on the rates of atom loss, the following upper limits were obtained for the rate constants: \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 \le 3 \times 10^{ - 17} {\rm cm}^{\rm 3} /{\rm molec - sec}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 \le 2 \times 10^{ - 15} {\rm cm}^{\rm 3} /{\rm molec - sec}$$\end{document} Observed reaction in the H—HNO3 system is at least partially due to an autocatalytic chain removal of both reactants. Diagnostic tests have suggested that OH, NO2, and NO3 are the chain carriers.
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• 22
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: A step perturbation (concentration-jump or solvent-jump) relaxation method is described for studying the rates of fast reactions, using nontransient observation in a steadystate flow system. Therelaxation time is determined from a single measurement of an integrated relaxation amplitude. Remeasurement of the rate of dimerization of aqueous rhodamine B is reported.
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• 23
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Reactions of ozone with simple olefins have been studied between 6 and 800 mtorr total pressure in a 220-m3 reactor. Rate constants for the removal of ozone by an excess of olefin in the presence of 150 mtorr oxygen were determined over the temperature range 280 to 360° K by continuous optical absorption measurements at 2537 Å. The technique was tested by measuring the rate constants k1 and k2 of the reactions (1) NO + O3 → NO2 + O2 and (2) NO2 + O3 rarr; NO3 + O2 which are known from the literature. The results for NO, NO2, C2H4, C3H6, 2-butene (mixture of the isomers), 1,3→butadiene, isobutene, and 1,1 -difluoro-ethylene are 1.7 × 10-1 4 (290°K), 3.24 × 10-17 (289°K), 1.2 × 10-1 4 exp (-4.95 ± 0.20/RT), 1.1 × 10-1 4 exp (-3.91 ± 0.20/RT), 0.94 × 10-1 4 exp ( -2.28 ± 0.15/RT), 5.45 ± 10-1 4 exp ( -5.33 ± 0.20/RT), 1.8 ×10-17 (283°K), and 8 × 10-20 cm3/molecule ·s(290°K). Productformation from the ozone-propylene reaction was studied by a mass spectrometric technique. The stoichiometry of the reaction is near unity in the presence of molecular oxygen.
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• 24
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Technical improvements have been made in the application of the phase shift method, recently developed and used in this laboratory to measure the absolute values of the rate constants of the reactions of O(3P) atoms with ethylene, propylene, 1-butene, and isobutene. More accurate rate constants have now been obtained for these olefins and themeasurements have been also extended to three additional olefins (cis-2-butene, trimethylethylene, and tetramethylene).The mean least squares values of the rate constants of the reactions of O(3P) with olefins at 26°C, expressed as k2 × 10-9 (1./mole2·sec), and their standard deviations are ethylene 0.43 ±0.05, propelene 2.02 ± 0.17, 1-butene 2.40 ± 0.32, isobutene 9.85 ± 1.34, cis-2-butene 9.00 ± 1.76, trimethylethylene 31.1 ± 3.0, and tetramethylethylene 44.4 ± 4.1. A Value of (5.78 ± 0.08) × 1010l.2/mole2·sec was obtained for the rate constant of the reaction O(3P) + NO + M, with M = N2O. Where comparison with the absolute rate constants in the literature is possible, agreement is very good, especiallywith some recent absolute values obtained by entirely different experimental techniques. Consistency with the relative rate constant of the O(3P) reactions with olefins previously determined in this laboratory, is excellent.
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• 25
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The kinetic equations for an 81-reaction model of a photochemical smog chamber have been solved using a complete numerical integration as well as a quasi-steady-state approximation (QSSA) procedure. The two sets of results differ markedly in their prediction of experimentally significant factors such as the hydrocarbon depletion rate and the ozone and (NO)x peaking times. The sources of the discrepancy are traced to the fact that the assumed steady-state conditions were not satisfied, leading to errors in the concentrations of intermediate radicals which in turn affect critical rates in the reaction model.The occurrence of such discrepancies in various types of reaction models, and with different QSSA strategies, is discussed, and it is concluded that the extent of such errors in QSSA calculations cannot be reliably predicted. Their impact on conclusions regarding reaction mechanisms and rate constants can surpass uncertainties in experimental data; conversely the credibility of predictions derived through QSSA calculations becomes highly suspect. Since recently devloped methods for complete numerical integration of systems of kinetic equations are now available, it is recommended that these be adopted in future work, and that the use of QSSA be abandoned.
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• 26
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The effect of added nucleophiles (methanol and 1,4-butanediol) on the steady-state kinetics of α-chymotryptic hydrolysis of a series of N-acetyl-L-amino acid methyl esters, R-CH(NHCOCH3)C(O)OCH3, has been studied. As a result, the rate and equilibrium constants of the ‘elementary’ steps of the enzyme process have been determined.It has also been demonstrated how the free energy-reaction coordinate profile changes if the structure (the size of the hydrocarbon chain) of the ‘chemically inert’ substrate fragment R is varied. The effects observed can be described by the following equation: where ΔGs and ΔGa are the free energies of formation of metastable intermediates, i.e., the enzyme-substrate complex and the acylenzyme, respectively, ΔG2≠ and ΔG3≠ are the free energies of activation for the chemical steps, i.e., enzyme acylation and acylenzyme hydrolysis, respectively; and ΔGtrans(R) is the free energy of transfer of substrate group R from water into a nonaqueous solvent.To explain the results obtained, a mechanism for enzyme-substrate interaction is suggested according to which the potential free energy of sorption of substrate group R on the enzyme is 2 ΔGtrans(R). Such a high gain in the free energy of hydrophobic interaction may only be realized if (a) in the free enzyme the sorption region has a thermodynamically unfavorable contact with the aqueous medium, and (b) water is forced out of the active center as a result of the hydrophobic interaction of substrate group R with the enzyme. Such a model is in agreement with the published x-ray data on the structure of the crystalline enzyme.The kinetic experiment has proved that not all the potential free energy of sorption is realized as binding force. Thus the true free energy of the binding of substrate group R with the protein does not exceed half the maximum value, both in the enzyme-substrate complex and acylenzyme.
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• 27
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Flash photolysis of 2,4,6-trinitrotoluene solutions (TNT) indicates a photochemically induced isomerization leading to the aci-quinoid isomer with an absorption maximum at 460 nm in nonpolar solvents, or the conjugate base of the aci-quinoid isomer with absorption maxima at 500, 540, and 630 nm in polar solvents. Both species, the quinoid isomer and the conjugate base, have transient existence and their identification was based on detailed spectroscopic and kinetic studies presented here. The magnitude of the negative charge on the transient conjugate base was determined with salt effect experiments and found to be equal to unity.
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• 28
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The exponential relaxation of CH3, produced by the reaction O + C2H4 → CH3 + HCO, to its steady-state concentration was quantitatively monitored after the reactants were mixed. The relaxation profiles yield the rate constant of the reaction O + CH3 → H2CO + H equal to (1.85 ± 0.28) × 10-10 cm3/molecule-sec at 300°K. Ancillary experiments yielded values for the rate constant for the reaction of O atoms with C2H4 at 300°K, the average of which is 7.7 × 10-12 cm3/molecule-sec. The experimental technique, which employs a fast-flow reactor coupled to a photoionization mass spectrometer, is described in detail and its potential discussed.
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Notes: First-order rate constants for formation of cyclohexanone and 2-cyclohexen-1-ol from 1,2-epoxycyclohexane and 1,2-epoxycyclohexane-3,3,6,6-d4 have been determined over the temperature range of 677-746°K. The observed kinetic isotope effects are used in an attempt to determine the mechanism for formation of products. A distinction between a biradical and a concerted mechanism for the alcohol formation could not be made. However, if a common biradical is the precursor of both cyclohexanone and 2-cyclohexenl-ol then the rate of ring closure of this biradical must be much faster than the rates of hydrogen transfer to give the ketone and the alcohol.
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Notes: Translation-vibration (T-V) and vibration-vibration (V-V) energy transfer processes in the N2-CO2 system were investigated using classical trajectory techniques. Two empirical interaction potentials were employed. One is comprised of independent, atom-atom Morse-type functions operating between nonbonded atoms. The other included these atom-atom Morse functions plus Coulombic terms to account for the quadrupole-quadrupole intertion. Both interaction potentials led to similar T-V results. However, the result that CO2(v3) is excited ∼103 times more efficiently than N2(v = 1) was obtained, which is at variance with existing analytical theories of T-V energy transfer employing purely repulsive short-range potentials. Different V-V energy transfer probabilities were obtained from the two interaction potentials. The most important finding is that only when electrostatic orientation effects are combined with short-range repulsive interactions is the near-resonant \documentclass{article}\pagestyle{empty}\begin{document}$${\rm N}_{\rm 2} {\rm (}v = {\rm 1)} + {\rm CO}_{\rm 2} {\rm (000)} \to {\rm N}_{\rm 2} {\rm (}v = {\rm 0)} + {\rm CO}_{\rm 2} {\rm (001)}$$\end{document} V-V transfer found to be the dominant energy transfer path. This interaction potential also crudely accounts for the negative temperature dependence observed for this near-resonant V-V transfer at low temperatures (300-1000°K).
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Notes: Oxidation of tetralin in the presence of tert-butyl hydroperoxide and tetralyl hydroperoxide, initiated with azobisisobutyronitrile, was studied at 60°C in order to examine the complications involved in the hydroperoxide method devised by Howard and Ingold. From literature data on absolute rate constants and our rates of oxidation, cross termination rate constants and contributions of each elementary propagation and termination step were computed. It was confirmed that this method was quite useful in determining the cross propagation rate constant, but it was also demonstrated that the rate of oxidation should be measured at very low conversion and with quite high concentrations of hydroperoxide, especially when the peroxy radical derived from the added hydroperoxide has a much lower termination rate constant than that from the oxidizing substrate.
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Notes: The complexes PdCl42-, PdCl3(H2O)-, and PdCl3(Ac)2-, in rapid equilibrium with each other under the adopted experimental conditions, react with ethylenediamine according to the experimental rate law \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \left\{ {\frac{k}{{\left[{{\rm H}^{\rm + } } \right]}} + \frac{{k'}}{{\left[{{\rm H}^{\rm + } } \right]\left[{{\rm Cl}^{\rm - } } \right]}} + \frac{{k''\left[{{\rm Ac}^{\rm - } } \right]}}{{\left[{{\rm H}^{\rm + } } \right]\left[{{\rm Cl}^{\rm - } } \right]}}} \right\}\left[{{\rm en}} \right]_{{\rm total}}$$\end{document} A reaction scheme is proposed involving the reaction of enH+ with each of the above species, and the specific rate constants are computed. The activation parameters are given.
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• 33
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Notes: The rate constant for the reaction I(2P1/2) + CH3I → I2 + CH3 has been reevaluated taking into account both collisional deactivation of excited iodine atoms and loss of I2 by I2 + CH3 → I + CH3I. The reevaluation is based upon data obtained (R. T. Meyer), J. Chem. Phys., 46, 4146 (1967) from the flash photolysis of CH3I using time-resolved mass spectrometry to measure the rate of I2 formation. Computer simulations of the complete kinetic system and a closed-form solution of a simplified set of the differential equations yielded a value of 6(± 4) × 106 1./mole-sec for the excited iodine atom reaction in the temperature region of 316 to 447 K. A slight temperature dependence was observed, but an activation energy could not be evaluated quantitatively due to the small temperature range studied. An upper limit for the collisional deactivation of I(2P1/2) with CH3I was also determined (2.4 × 107 1./mole-sec).
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• 34
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Notes: The four species in the title were decomposed under VLPP conditions at temperatures in the vicinity of 1100°K. Three model transition states were constructed that fit the low-pressure data thus obtained and that also yield (1) E298 = ΔE298; (2) E1100 = ΔE1100; (3) log A1100 = 16.4 per C-C bond broken. The predictions of these models as to values of the high-pressure rate constants for bond scission and the reverse rate constants (radical combination) are compared with existing data.
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• 35
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Notes: The kinetics of the thermal decomposition of diallylamine to propylene and prop-2-enaldimine have been studied in the gas phase in presence of an excess of methylamine over the temperature range of 532.7 to 615.6°K, using a static reaction system. Methylamine reacted with the unstable primary product prop-2-enaldimine, forming the thermally stable N-methyl prop-2-enaldimine.First-order rate constants, based on the internal standard technique, fit the Arrhenius relationship log k(s-1) = (11.04 ± 0.13) - (37.11 ± 0.33 kcal/mole)/2.303 RT. They were independent on the initial total pressure (46-340 torr), the initial pressure of diallylamine (9.2-65 torr), or methylamine as well as the conversion attained. Despite an apparent surface sensitivity, the reaction is essentially homogeneous in nature as demonstrated by experiments carried out in a packed reaction vessel.The observed activation parameters for the title reaction together with those observed earlier for triallylamine and allylcyclohexylamine are consistent with the proposed concerted reaction mechanism involving a cyclic 6-center transition state. The observed substituent effects suggest a nonsynchronous mode of bond breaking and bond formation.
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• 36
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Notes: The kinetics of the reaction between ozone and allene (A) were studied in the range of 226 to 325°K in the gas phase. Initial O3 pressures varied from 0.01 to 0.7 torr and allene pressures varied from 0.05 to 6 torr. At the higher initial O3 pressures the most important product was O2 followed by CO, H2O, CO2, and C2H4. Oxygen balances averaging about 110% were obtained, which implies that no important oxygenated products were missed. However, carbon balances were only about 50% and hydrogen balances were even less, so that unidentified hydrocarbons were presumably formed. The rate law found was - d[O3]/dt = k1[O3][A] + k2a[O3]2[A]/[O3]0 where log k1(M-1sec-1) = 6.0 ± 0.7 - (5500±1000)/2.30RT and log k2a(M-1sec-1) = 6.9 ± 0.7 - (6200 ± 800/2.30RT). A mechanism is proposed which accounts for the rate law and the observed stoichiometry of O2 formed-O3 used. This involves a heterogeneous catalyzed decomposition of O3. The rate constant k1 is identified with the primary addition reaction A + O3 → AO3, and this rate constant is compared with those from other O3 addition reactions.
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• 37
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Notes: The rate constants of liquid-phase hydrogen abstraction by chlorine atoms from 1,2-C2H4Cl2 relative to those of addition to C2HCl3 and to C2Cl4 and to that of hydrogen abstraction from cyclohexane have been measured between 250 and 345°K. Assuming a zero activation energy for the addition reactions permits one to calculate the corresponding values for the liquid-phase hydrogen abstraction from the chlorinated ethanes. These values are discussed and compared with the gas-phase data.
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• 38
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Notes: Competitive studies of the reactions of ground-state oxygen atoms, generated by mercury-photosensitized decomposition of nitrous oxide, have been carried out with ethylene and all the fluoroethylenes using 2-(trifluoromethyl)-propene as reference compound. From measurements at 25°C and 150°C relative rate constants have been determined and used to calculate the Arrhenius parameters shown in the following table: TextOlefin\documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{A_{{\rm olefin}} }}{{A_{{\rm 2TFMP}} }}$$\end{document}ΔERef\documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{A_{{\rm olefin}} }}{{A_{{\rm C}_{\rm 2} {\rm H}_{\rm 4} } }}$$\end{document}ΔEC2H4CH2—CH21.10-1.18(1.0)(0)CH2—CHF1.030.840.942.02CH2—CF20.711.490.652.67CHF—CHF (cis-)1.231.921.123.10CHF—CHF (trans-)1.400.791.271.97CF2—CHF1.060.000.961.22CF2—CF20.86-3.220.78-2.04ΔERef = Eolefin - E2TFMP and ΔEC2H4 = Eolefin - EC2H4. Units are kJ/mole.The results are compared with corresponding data for other atoms and radicals, and discussed in terms of the electronic changes produced in the double bond by fluorine substitution, and in relation to the nature of the transition state.
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• 39
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Notes: The photolysis of azocyclohexane, carbon tetrachloride, and cyclohexane at 360 nm has been investigated over a wide temperature range. At moderate temperatures a chain reaction ensues from which the following approximate rate constants could be determined assuming 2CCl3. → C2Cl6, k5 = 109.7 (303-673K): The really striking feature of the results is that they show that termination in bicyclohexyl [reaction (7)] is extremely slow: The root-mean-square rule for estimating the cross-combination rate is also followed.The photolysis of carbon tetrachloride and cyclohexane at 250 nm has also been investigated. The reaction is complicated by the occurrence of two concurrent photolytic processes, the main one yielding trichloromethyl radicals and chlorine atoms, and the subsidiary one yielding dichlorocarbene and molecular chlorine. Nonetheless the results from this reaction can be interpreted in the medium temperature range 360-430K, where long chains are present, in terms of the rate constants derived from the azocyclohexane system.
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• 40
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Notes: Predictions of the “redox” and “complex” schemes for the Fe3+ catalyzed decomposition of H2O2 have been compared with published and new experimental data by numerical integratior of the appropriate complete sets of differential equations. Apparent discrepancies for the redox scheme at high Fe3+/H2O2 ratios are shown to disappear in the complete treatment, and inconsistencies of the complex scheme with both kinetic data and spectroscopic measurements are pointed out.
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• 41
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Notes: The photochemistry of 1,1,1-trifluoromethylazomethane has been partially characterized. The quantum yield for N2 formation from photolysis at 366 nm and room temperature was unity at low pressure and decreased to 0.5 at 630 torr. At room temperature the principal products were C2H6, C2F6, CH3CF3 (or CH2CF2 + HF at reduced pressures), plus substituted hydrazines, which mainly arise from addition of CF3 to the parent followed by combination of these radicals with CH3 or CF3. These fluorinated methyl hydrazine products detract from the general utility of CF3-N2-R compounds as sources for simultaneous study of the chemistry of CF3 and R radicals. At room temperature the hydrazine products accounted for more than 50% of the total yield; however, these products can be reduced by lowering the temperature and at 195°K their yields are negligible. The quantum yield for intramolecular (direct) formation of CH3CF3 + N2 was shown to be ≤0.002.
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• 42
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Notes: The decomposition of acetylenedicarboxylic acid in acetophenone was studied in the temperature range of 100-130°C. The rate constants and activation parameters for the consecutive pair of first-order steps (each yielding carbon dioxide) were calculated. Hydrogen kinetic isotope effects were also studied. Comparisons were made with the decompositions of oxalic acid and malonic acid. An intramolecular H—C transfer is believed to be the main part of the reaction coordinate in addition to the C—C bond breaking.
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• 43
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Notes: The reaction of O(3P), prepared from the Hg photosensitization of N2O, with C2HCl3 was studied at 25°C. The products of the reaction in the absence of O2 were CO, CHCl3, and polymer (as well as N2 from the N2O). The quantum yields of CO and CHCl3 were 0.23 ± 0.01 and 0.14 ± 0.05, is respectively independent of reaction conditions. The reaction mechanism is with k14a/k14 = 0.23, where k14a + k14b. Most of the HCl and CCl2 combine to form CHCl3, but some other products must also be formed to account for the difference in the CO and CHCl3 quantum yields. The C2HCl3O* adduct polymerizes without involving additional C2HCl3 molecules, since the quantum yield of C2HCl3 disappearance, —Φ{C2HCl3}, was about 1.0 at high values of [N2O]/[C2HCl3]. The rate coefficient for the reaction of O(3P) with C2HCl3 is 0.10 that for the reaction of O(3P) with C2F4.In the presence of O2 the free radical chain oxidation occurs because of the reaction The main product is CHCl2CCl(O) with smaller amounts of CO and CCl2O, and some CO2. The chain lengths were long and values of — Φ {C2HCl3} up to 90 were observed.
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Notes: The thermal decomposition of t-butylmethyl ether has been studied using the VLPP technique. The recommended Arrhenius parameters for the molecular elimination, reaction (1), are A(800°K) = 101 3, 9 sec-1 and Ea (800°K) = 59.0 ± 1.0 kcal/mole. No radical reactions occur under the conditions used. These parameters are in good agreement with earlier experimental work and with theoretical estimates of both A and E.
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Notes: Chloroethanes react with aqueous caustic to yield either elimination or substitution products. The reaction rates were measured for the dichloroethanes, trichloroethanes, tetrachloroethanes, and pentachloroethane between 283 and 353°K. The constants of HCl eleminations referring to the rate equation \documentclass{article}\pagestyle{empty}\begin{document}$$r = k[{\rm OH}^{\rm - }][{\rm dissolved \,substrate]}$$\end{document} are given by \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,2 - C}_{\rm 2} {\rm H}_{\rm 4} {\rm Cl}_{\rm 2} {\rm }\,k = 10^{10.99 \pm 0.03} \exp (- 23,000 \pm 50RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,2 - C}_{\rm 2} {\rm H}_{\rm 3} {\rm Cl}_{\rm 3} {\rm}\,k = 10^{13.99 \pm 0.03} \exp (- 22,400 \pm 50/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,1,2 - C}_{\rm 2} {\rm H}_{\rm 2} {\rm Cl}_{\rm 4} {\rm }\,k = 10^{15.45 \pm 0.14} \exp (- 25,800 \pm 210/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,2,2 - C}_{\rm 2} {\rm H}_{\rm 2} {\rm Cl}_{\rm 4} {\rm }\,k = 10^{16.40 \pm 0.05} \exp (- 22,550 \pm 70/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm C}_{\rm 2} {\rm HCl}_{\rm 5} {\rm }\,k = 10^{12.50 \pm 0.08} \exp (- 15,200 \pm 110/RT)$$\end{document} all rate constants being in 1./mole·s and R in cal/mole· deg.With ethyl chloride, 1,1-dichloroethane, and 1,1,l-trichloroethane, the elimination is not observed and a slow substitution takes place. The influence of chlorine substituents on both sides of the molecule on mechanism and rate parameters is discussed.
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Notes: The homogeneous pyrolysis of 2-butene subjected to shock heating was studied in the limit of high pressures by a relative rate technique. Over the temperature range of 1150-1325°K nearly equal amounts of methane, propylene, and butadiene were formed starting with either the cis- or trans-2-butene, while isomerization remained far from equilibrium. The results are consistent with a simple free radical mechanism for which we find \documentclass{article}\pagestyle{empty}\begin{document}$$k^\infty [{\rm C}_4 {\rm H}_8 \mathop \rightarrow\limits_{cis} {\rm CH}_3 + {\rm C}_3{\rm H}_5] = 10^{16} \exp (-80,000/RT)\sec^{-1}$$\end{document} as the initial rate-limiting step.
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Notes: Study of the reaction by very-low-pressure pyrolysis (VLPP) in the temperature range of 550-850°K yields for the high-pressure Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }\,k_{\rm 1} = (15.6 \pm 0.5) - (36.0 \pm 1.0)/\theta {\rm \,(sec}^{{\rm - 1}})$$\end{document} where θ = 2.303RT in kcal/mole. These in turn yield for the high-pressure second-order recombination of tBu + NO, k-1 = (3.5 ± 1.7) × 109 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E4 ≥ 4.2 kcal/mole. The bond dissociation energy DHo (tBu-NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free-volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8-200 torr showed an extremely rapid inhibition by products and a very complex set of products.
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Notes: The chemical reactions of SO2(3B1) molecules with cis- and trans-2-butene have been studied in gaseous mixtures at 25°C by excitation of SO2 within the SO2(3B1) → SO2(+, 1A1) ‘forbidden’ band using 3500-4100-Å light. The initial quatum yields of olefin isomerization were determined as a function of the [SO2]/[2-butene] ratio and added gases, He and O2. The kinetic treatment of these data suggests that there is formed in the SO2(3B1) quenching step with either cis- or trans-2-butene, some common intermediate, probably a triplet addition complex between SO- and olefin. It decomposes very rapidly to form the 2-butene isomers in the ratio [trans-2-butene]/[cis-2-butene] = 1.8. In another series of experiments SO2 was excited using a 3630 ± 1-Å laser pulse of short duration, and the SO2(3B1) quenching rate constants with the 2-butenes were determined from the SO2(3B1) lifetime measurements. The rate constants at 21°C are (1.29 ± 0.18) × 1011 and (1.22 ± 0.15) × 1011 l/mole·sec with cis-2-butene and trans-2-butene, respectively, as the quencher molecule. Within the experimental error these quenching constants equal those derived from the quantum yield data. Thus the rate-determining step in the isomerization reaction is suggested to be the quenching reaction, presumably the formation of the triplet SO2-2-butene addition complex. In a third series of experiments using light scattering measurements, it was found that the aerosol formation probably originates largely from SO3 and H2SO4 mist formed following the reaction SO2(3B1) + SO2 → SO3 + SO(3Σ-). Aerosol formation from photochemically excited SO2-olefin interaction is probably unimportant in these systems and must be unimportant in the atmosphere.
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Notes: The thermal isomerization of 1,1-divinylcyclopropane has been investigated in the gas phase in the temperature range of 238 to 288°C and for pressures in the range of 4 to 12 torr. The isomerization to 1-vinylcyclopentene is homogeneous and kinetically first order and almost certainly unimolecular. The rate constants yield the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k({\rm s}^{ - 1} {\rm)} = 13.53 \pm 0.13 - (42.45 \pm 0.33{\rm \,kcal/mole})/RT\,{\rm In 10}$$\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k({\rm s}^{ - 1} {\rm)} = 13.53 \pm 0.13 - (117.6 \pm 1.4{\rm \,kJ/mole})/RT\,{\rm In 10}$$\end{document} The assumption of a similar transition state for this isomerization with that of l-methyl-l-vinylcyclopropane leads to a value for an alkylpentadienyl radical stabilisation energy of 19.2 ± 1.6 kcal/mole (80.4 ± 6.7 kJ/mole), and this value is compared with other estimates.
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Notes: The following net processes occur in a system containing chlorine and hydrogen bromide: \documentclass{article}\pagestyle{empty}\begin{document}$$(1)\begin{array}{*{20}c} {} & {} \\ \end{array}{\rm Cl}_{\rm 2} + {\rm HB}r \to {\rm BrCl + HCl}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$(2)\begin{array}{*{20}c} {} & {} \\ \end{array}{\rm BrCl + HB}r \to {\rm Br}_{\rm 2} {\rm + HCl}$$\end{document} These reactions have been followed spectrophotometrically in a gas phase stopped flow apparatus. The first two reactions are strongly surface catalyzed on untreated glass or quartz, but are much slower if the cell surface has been covered with silicone and photochlorinated. Rates in such systems are first order in each reactant, and comparable limiting rate constants have been obtained in cells with different methods of preparing the surfaces and with different surface-to-volume ratios. These experimental rate constants must be equal to or greater than those of the homogeneous bimolecular reactions. Then limiting rate constants at 35°C in liters per mole per second are k1 ≤ 0.8, k 2 ≤ 15, and k3 ≤ 0.04. Reactions of HI with Cl2, Br2, and ICl are all much faster than reaction (2). These observations and those of other diatomic molecule reactions can be rationalized if halogen and hydrogen halide molecules react through a transition state in which the hydrogen atom is near the center of a triangle of three halogen atoms.
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Topics: Chemistry and Pharmacology
Notes: A kinetic study of lead atoms in the spin orbit states, Pb(63P1) and Pb Pb(63P2), 0.969 and 1.320 eV, respectively, above the 63P0 ground state, has been carried out by atomic absorption spectroscopy. The electronically excited lead atoms were generated by the pulsed irradiation of lead tetraethyl and monitored photoelectrically by time-resolved attenuation of resonance radiation. The decay of the two atomic states has been studied in the presence of He, Ar, H2, D2, N2, O2, CO, NO, CO2, N2O, CH4, C2H4, C2H2 CF4, SF6, and PbEt4, and rate constants for the collisional quenching by these gases are reported. The resulting data are compared with those for the deactivation of other atomic spin orbit states of comparable energy. In general, the higher energy state, Pb(63P2), is found to be deactivated more rapidly. It would appear that the magnitude of the electronic energy to be transferred on collision governs the rates of quenching, at least where a weak interaction potential is involved, and that for most gases, deactivation of Pb(63P2) proceeds via Pb(63P1).
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• 56
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The effect of reactant self-heating or cooling upon rate data is considered, and three approaches to the problem of obtaining valid kinetic parameters are described in detail. A comparison of these approaches emphasises the need to assess and allow for thermal effects during the initial planning of kinetic experiments if satisfactory results are to be acquired. An integrated rate expression is given for use with nonisothermal data, and is used to provide correction factors for rate constants which have been derived without allowance for thermal effects.
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• 57
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: A study has been made of the unimolecular decomposition of the vibrationally excited molecule CF2DCFH2*, formed from the combination of CF2D and CFH2 radicals. The α,β-elimination channels lead to the products cis- and trans-CFDCFH and CF2CH2 and H(D)F. The α,α-elimination channel produces cis and trans-CFHCFH and DF. The pressure dependencies of the various isomer ratios have been examined. For the α,α elimination the energy partitioning pattern is such that subsequent isomerization of the olefin product can occur. This, and previous work on CDCl2CH2Cl*, clearly show that the energy partitioning in α,α and α,β eliminations is very different. It is tentatively concluded that HF (from the CFH2 group) and HD eliminations also take place.
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• 58
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: A low-temperature matrix isolation method has been developed which makes possible the isolation and detection of HO2 radicalsfrom a gas-phase radical chain-reaction system containing atomic H, O and OH radicals as well. The formation of HO2 radicals is demonstrated in the rarified hydrogen flame. The same radicals are observed to exist during the slow oxidation reaction of hydrogen between the second and third inflammation limitsThe kinetics of accumulation of HO2, H2O2, and H2O has been studied as a function of total pressure, composition of reacting mixtures, temperature, and diameter and the treatmentof the surface of the reaction vessel. It has been established that in a reactor treated with boric acid, the concentration of HO2 radicalsis in the order of 101 2-101 4 particles/cm3. The kinetic relationship obtained confirms the necessity of including the following step in the mechanism of slow oxidation of hydrogen: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm HO}_2 {\rm + }\;{\rm HO}_{{\rm 2 }} = {\rm H}_{\rm 2} {\rm O}_{\rm 2} {\rm + O}_{\rm 2}$$\end{document}For a quantitative description of the experimental results, calculationsof the complete mechanism of the slow reaction are performed by computer methods. The values of the rate constants of the elementary reactions that enter into the mechanism proposed were taken from published data. Some of them were varied by small intervals to give a better agreement with experimental values. The agreement justifies the mechanism proposed for the experimental conditions employed.
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• 59
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Shock tube experiments on the decay of OH-radical concentration after shock-initiated combustion of H2:O2:Ar = 10:1:89 mixtures were analyzed to give the rate constant 1 × 1015 cm6mol-2s-1for the reaction H + H + Ar = H2 + Ar overthe temperature range 1300 to 1700 K.
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• 60
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Very strong laser emission at 5 μm was detected when SO2 and CHBr3 were flash photolyzed in the vacuum ultraviolet (λ ≥ 165 nm) in the presence of a large amount of diluent (SF6, He, or Ar). About 110 vibration-rotation transitions ranging from Δv = 18 → 17 to 3 → 2, except 16 → 15, were identified. The primary reactions leading to the CO stimulated emission are as follows: The product analysis results and the variation of laser intensity with flash energy and SO concentration indicate that the following side reactions are also occurring. Addition of a small amount of O2 enhances the laser output by both eliminating these side reactions and simultaneously producing vibrationally excited CO via reaction (8), which has been previously shown to generate CO stimulated emission. The effects of various reactive (NO and H2) and inert (He, Ar, SF6, CO, N2, N2O, and CO2) gases have been examined. All additives (P ≤ 20 torr), except NO and H2, increase the total laser output. N2O enhances the power most efficiently, whereas CO, N2, and CO2 are less effective and have similar efficiencies. The enhancement of the laser intensity by these near-resonant gases is ascribed to the depletion of CO population at lower levels which thus increases the rates cascading from higher levels. NO and H2 quench the laser output by chemically reducing the concentration of the CH radical.
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• 61
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The rate constants for the replacement of water from the inner-coordination shell of Co(NH3)5OH23+, I, by dimethyl sulfoxide (DMSO) as DMSO gradually replaced water in the solvation shell of I were found to approach, and finally equal, the water-exchange rate constant of I in aqueous media in accordance with expectation for a dissociative mechanism. Also the rate constants for the replacement of DMSO from the innercoordination shell of Co(NH3)5DMSO3+, II, by water as water replaced DMSO in the solvation shell of II were found to approach, and approximately equal, the DMSO-exchange rate constant for II in liquid DMSO in accordance with expectation for a dissociative mechanism.The DMSO-exchange rate constant for II in liquid DMSO was determined and found to be equal to (3.6 ± 0.8) × 10-4 sec-1 at 45°C.The dissociation quotient, [II] [NO3-]/[Co(NH3)5NO32+], was found to be equal to 0.28 ± 0.11 M at 45°C by NMR methods. The pseudo first-order rate constants for anation of II by NO3- and the solvation of Co(NH3)5NO3 2+ by DMSO were determined at various temperatures.
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• 62
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Electronically excited oxygen atoms O(21D2) have been generated by the pulsed irradiation of ozone in the Hartley-band continuum and monitored photoelectrically in absorption by time-resolved attenuation of atomic resonance radiation at λ = 115.2 nm [O(31D2°) → O(21D2)]. Collisional quenching of the excited atom has been investigated for all the noble gases, and the first absolute values for the second-order deactivation rate constants are reported. The resulting rate data are discussed in terms of a curve-crossing mechanism based on existing spectroscopic data for the noble gas oxides. The absolute rate constants are compared with previous relative rate data for the deactivation of O(21D2) by the noble gases.
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• 63
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The photochemistry of p-fluoranil in dioxane was studied by electron spin resonance (ESR) and the ESR-rotating sector technique. The transient photoradical is identified as the p-tetrafluorobenzosemiquinone neutral radical with a hyperfine splitting of 1.1 gauss for the hydroxy proton and the fluorine hyperfine splittings of 3.8 and 14.1 gauss for the meta and ortho fluorines, respectively. The radicals decayed by self-disproportionation with a second-order rate constant at room temperature of approximately 3.2 × 109M-1s-1. The activation energy of the decay process is found to be about 2.4 ± 0.4 kcal/mole.
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• 64
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
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• 65
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The kinetics of N-phenylphthalamic acid and of N-phenylphthalimide hydrolysis in aqueous solutions of sulfuric acid has been studied. A reaction mechanism is proposed implying that unreactive forms of the reactant appear by protonization of the amide bond at the carbonyl oxygen and by dissociation of the o-carboxyl group (N-phenylphthalamic acid). Attack of the nonprotonized amide bond by the hydroxonium ion is suggested to be the rate-limiting step.
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• 66
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: Vibrationally excited pentyl-1, -2, and -3 radicals were formed selectively by the addition of thermal H atoms to the various pentene isomers with approximately 47 kcal/mole of vibrational energy. Decomposition products other than those expected, along with their pressure dependences, support the fact that either 1,2 or 1,3 hydrogen migrations with either a 3- or 4-member cyclic transition state is occurring with a ka of approximately 3 × 105 or 6 × 105 sec-1. A corresponding critical energy of 33 or 31 kcal/mole is found.
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• 67
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New York, NY : Wiley-Blackwell
ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
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• 68
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ISSN: 0538-8066
Keywords: Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology
Notes: The substitution of N-alkyl substituted ethylenediamines for chloride ions in the rapidly equilibrating system \documentclass{article}\pagestyle{empty}\begin{document}$${\rm PdCl}_{\rm 4} ^{{\rm 2 - }} {\rm + H}_{\rm 2} {\rm O}\rightleftharpoons{\rm PdCl}_{\rm 3} ({\rm H}_2 {\rm O)}^{\rm - } + {\rm Cl}^{\rm - }$$\end{document} has been investigated in aqueous acid medium. The kinetic data can be accommodated by the general rate law \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \left\{ {\frac{k}{{\left[{{\rm H}^{\rm + }} \right]}} + \frac{{k'}}{{\left[{{\rm H}^{\rm + } } \right]\left[{{\rm Cl}^{\rm - } } \right]}}} \right\}\left[{{\rm N}_{\rm n} {\rm N}_{\rm m} {\rm en}} \right]_{{\rm total}}$$\end{document} where n = 0, 1, or 2 and m = 0, 1, or 2, depending on whether none, one, or two methyl groups are attached to the two nitrogen atoms of ethylenediamine. Reaction with the most heavily substituted ethylenediamine, namely, N2N2en discloses a change of the mentioned rate law to \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \left\{ {\frac{{k''}}{{\left[{{\rm H}^{\rm + } } \right]}} + \frac{{k'''\left[{{\rm Cl}^{\rm - } } \right]}}{{\left[{{\rm H}^{\rm + } } \right]}}} \right\}\left[{{\rm N}_{\rm 2} {\rm N}_{\rm 2} {\rm en}} \right]_{{\rm total}}$$\end{document} on going from a lower to a higher chloride ion concentration range. This change in the mathematical form of the rate law can be explained in terms of an ion-pair association of N2N2enH+ and free chloride ions.