摘要:

AbstractRelative Arrhenius parameters have been determined for the addition of trifluoromethyl radicals to vinyl chloride (XCl), vinyl bromide (XBr), acrylonitrile (XCN), methyl vinyl ketone (XCOCH3), 2‐methylbut‐2‐ene, and to iso‐butene, taking the rate of addition to ethylene as standard. Addition occurred virtually exclusively at the unsubstituted end of all the olefins. The relative rates of addition at 164°C show very little variation. The preexponential terms for addition to the CH2ends are constant within experimental error, and the small variations in rate are due principally to the activation energy term. The present results are put on an absolute scale using the previously determined Arrhenius parameters for addition to ethylene and are compared with data for other similar monomers deter

ISSN:0538-8066    

DOI:10.1002/kin.550100402

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY

摘要:

AbstractThe reactons of (CO2)2+and (CO)2+with various additives have been investigated using the NBS high‐pressure photoionization mass spectrometer at total pressures of 0.4–1.0 torr of either CO2or CO. The additives include CH4, CD4, C2H2, O2, H2O,15,14N2O, and CO in both CO2and13CO2. Second‐ and third‐order rate coefficients based on an ambipolar diffusion model are reported for 25 separate reaction pairs at 295°K, as well as sequential cationic reaction mechanisms. An approximate value of 225 ± 3 kcal/mol (941 ± 13 kJ/mol) was derived for ΔHf(CO)2+based on the kinetics observed in various CO‐additive mixtures. Some projections regarding the utility of the data under other conditions are

ISSN:0538-8066    

DOI:10.1002/kin.550100403

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY

摘要:

AbstractAtomic resonance absorption spectrometry with a nonreversed fluorine resonance lamp (∼95 nm) has been used to study the kinetics of elementary reactions of ground state F2PJatoms in a discharge‐flow system. The following rate constants (in cm3/molec·sec)All rate constants are given with 1.5 σ.were determined at 298° K:The reaction F2PJ+ HCl(1) was found to give J‐excited Cl2P1/2atoms with a product branching ratio [Cl2P1/2]/[Cl2P3/2

ISSN:0538-8066    

DOI:10.1002/kin.550100404

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY

摘要:

AbstractThe pyrolysis of ethylene–propylene and ethylene–isobutene mixtures has been studied in a static system over the temperature range of 682°–754° K and for initial pressures of each olefin of 33–300 torr. The following molecular ene reactions were observed and the rate constants measured:Using thermodynamic data, rate constants for the corresponding retro‐ene decomposition reactions were calculated and compared to kinetic data reported for similar compounds. Other products were formed by radical chain processes, the main higher molecular weight ones being cyclopentene and 1‐methylcyclopentene. A mechanism involving addition of allyl radicals is suggested for the formation of t

ISSN:0538-8066    

DOI:10.1002/kin.550100405

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY

摘要:

AbstractThe kinetics of the deprotonation of tropaeolin O by OH−ions was investigated between 9° and 30°C, and by OD−ions at 24.7°C. The pH range was 10.7–12.5, and the ionic strength 0.1Mthroughout. All results were obtained by the temperature jump method. On the basis of a mechanism suggested earlier, rate constantsk31for the reaction between OL−and the internally bonded weak acid andk32for the opening of the internal hydrogen bond were evaluated. The activation energies in ordinary water were found to be ΔH≠31= 3.6 kcal/mol, ΔS≠31= –19 eu, and ΔH≠32= 27 kcal/mol, ΔS≠32= 46 eu. The kinetic isotope effect wask31 H 2O/k31 D 2O∼ 1.5 andk32 H 2O/k32 D 2O∼ 0.9. The unusual results for reaction pathare

ISSN:0538-8066    

DOI:10.1002/kin.550100406

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY

摘要:

AbstractA simple computerized method using APL is described which gives the rate constants for systems obeying the rate law –d[A]/dt=k1[A][B]+k2[A]m[B]lfrom sets of concentrations and times. Applications are discusse

ISSN:0538-8066    

DOI:10.1002/kin.550100407

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550100408

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550100409

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550100401

出版商:John Wiley&Sons, Inc.    

年代:1978

数据来源: WILEY