摘要:

AbstractThe effect of cationic and anionic surfactants on the reaction of Basic Blue 3 (2,7‐bis(diethylamino)phenazoxonium chloride, 1) with hydroxide ion has been studied. Cetyltrimethylammonium bromide (CTAB), cetyl and tetradecyltrimethylammonium chloride (CTAC and MTAC) enhance the rate of basic hydrolysis whereas sodium dodecyl sulfate (SDS) has an inhibitory effect. The extent of micellar catalysis is reduced by the addition of organic solvents. The results have been analyzed on the basis of the pseudophase ion‐exchange model [1

ISSN:0538-8066    

DOI:10.1002/kin.550220202

出版商:John Wiley&Sons, Inc.    

年代:1990

数据来源: WILEY

摘要:

AbstractAn aged kineticist was awakened in 1989 from a 50‐year slumber. After arduous study he sized‐up the present situation, with occasional reflections on the state of knowledge in 1

ISSN:0538-8066    

DOI:10.1002/kin.550220203

出版商:John Wiley&Sons, Inc.    

年代:1990

数据来源: WILEY

摘要:

AbstractThe pyrolysis products formed during the isothermal decomposition of HMX at 211°C are H2O, HCN, CO, CH2O, NO, N2O, methylformamide, C2H6N2O, octahydro‐1‐nitroso‐3,5,7‐trinitro‐1,3,5,7‐tetrazocine, and a nonvolatile residue. The temporal behaviors of these products during the decomposition are presented. The method for using time‐of‐flight (TOF) velocity spectra to assist mass‐spectrometry measurements in identifying the different gaseous products formed from the pyrolysis of a material by determining the approximate molecular weights of the different gaseous products contributing to the different m/z values in the mass spectrum of the mixture is described. The ion fragmentation of HMX as a function of electron energy shows complete fragmentation of the HMX molecular ion for electron energies ≥ 12.4 eV. No fragments from the pyrolysis of HMX other than those mentione

ISSN:0538-8066    

DOI:10.1002/kin.550220204

出版商:John Wiley&Sons, Inc.    

年代:1990

数据来源: WILEY

摘要:

AbstractThe method for determining the rates of formation of gaseous pyrolysis products during thermal decompositions by simultaneous thermogravimetric modulated beam mass spectrometry is presented. The analysis procedure that handles both molecular and continuum flow from the reaction cell is described. The technique is illustrated with the isothermal decomposition of HMX. The temporal behaviors of the rates of formation of the pyrolysis products, H2O, HCN, CO, CH2O, NO, N2O, methylformamide, C2H6N2O, and octahydro‐1‐nitroso‐3, 5, 7‐trinitro‐1, 3, 5, 7‐tetrazocene, formed during the isothermal decomposition of HMX at 211°C, are presented. The results show that a complex condensed‐phase reaction mechanism controls the

ISSN:0538-8066    

DOI:10.1002/kin.550220205

出版商:John Wiley&Sons, Inc.    

年代:1990

数据来源: WILEY

摘要:

AbstractThe photolysis oftrans‐3,4‐dimethylcyclopentanone has been investigated in the gas phase at 100°C using light of 206 and 193 nm. The photolytic products are propene, 1,2‐dimethylcyclobutane, and the butene isomers. Small quantities of 3,4‐dimethylpent‐4‐enal were also detected. Relative yields of these products were determined as a function of the ketone pressure and also of that of added nitrogen. A mechanism for the photochemical decomposition based on that suggested for the photolysis of cyclopentanone using short wavelength radiation, is consistent with the experimental results and is simpler than that required to account for the long wavelength photolysis repo

ISSN:0538-8066    

DOI:10.1002/kin.550220206

出版商:John Wiley&Sons, Inc.    

年代:1990

数据来源: WILEY

摘要:

AbstractA detailed master equation simulation has been carried out for the thermal unimolecular decomposition of C6H10in a shock tube. At the highest temperatures studied experimentally [J. H. Kiefer and J. N. Shah, J. Phys. Chem., 91, 3024 (1987)], the average thermal vibrational energy is greater than the reaction threshold and therefore 〈ΔE〉 (up and down steps) is positive for molecules at that energy, rather than negative; the converse is true at lower temperatures. The calculated incubation time, in which the decomposition rate constant rises to 1/e of its steady state value, is found to be only weakly dependent on temperature (at constant pressure) between 1500 K and 2000 K and to depend almost exclusively on 〈ΔE〉d(down steps, only), and not on collision probability model. Simulations of the experimental data show the magnitude of 〈ΔE〉ddepends weakly on assumed collision probability model, but is nearly independent of temperature. The second moment 〈ΔE〉½is found to be independent of both temperature and transition probability model. The experimental data are not very sensitive to the possible energy‐dependence of 〈ΔE〉dfor a wide range of assumptions. It is concluded that the observed experimental “delay times” probably can be identified with the incubation time; further experiments are desirable to test this possibility and obtain more direct

ISSN:0538-8066    

DOI:10.1002/kin.550220207

出版商:John Wiley&Sons, Inc.    

年代:1990

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550220201

出版商:John Wiley&Sons, Inc.    

年代:1990

数据来源: WILEY