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Title: Kinetic and Numerical Study on the Effects of Di- tert -butyl Peroxide Additive on the Reactivity of Methanol and Ethanol

Authors:
 [1];  [1];  [2];  [3];  [1]
  1. Engine Research Center, University of Wisconsin—Madison, 1500 Engineering Drive, Madison, Wisconsin 53705, United States
  2. State Key Laboratory of Engines, Tianjin University, No. 92 Weijin Road, Nankai District, Tianjin 300072, China
  3. School of Energy and Power Engineering, Dalian University of Technology, Dalian 116024, China
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1384005
DOE Contract Number:
SC0001198
Resource Type:
Journal Article
Resource Relation:
Journal Name: Energy and Fuels; Journal Volume: 28; Journal Issue: 8; Related Information: CEFRC partners with Princeton University (lead); Argonne National Laboratory; University of Connecticut; Cornell University; Massachusetts Institute of Technology; University of Minnesota; Sandia National Laboratories; University of Southern California; Stanford University; University of Wisconsin, Madison
Country of Publication:
United States
Language:
English
Subject:
biofuels (including algae and biomass), hydrogen and fuel cells, combustion, carbon capture

Citation Formats

Wang, Hu, Dempsey, Adam B., Yao, Mingfa, Jia, Ming, and Reitz, Rolf D.. Kinetic and Numerical Study on the Effects of Di- tert -butyl Peroxide Additive on the Reactivity of Methanol and Ethanol. United States: N. p., 2014. Web. doi:10.1021/ef500867p.
Wang, Hu, Dempsey, Adam B., Yao, Mingfa, Jia, Ming, & Reitz, Rolf D.. Kinetic and Numerical Study on the Effects of Di- tert -butyl Peroxide Additive on the Reactivity of Methanol and Ethanol. United States. doi:10.1021/ef500867p.
Wang, Hu, Dempsey, Adam B., Yao, Mingfa, Jia, Ming, and Reitz, Rolf D.. Fri . "Kinetic and Numerical Study on the Effects of Di- tert -butyl Peroxide Additive on the Reactivity of Methanol and Ethanol". United States. doi:10.1021/ef500867p.
@article{osti_1384005,
title = {Kinetic and Numerical Study on the Effects of Di- tert -butyl Peroxide Additive on the Reactivity of Methanol and Ethanol},
author = {Wang, Hu and Dempsey, Adam B. and Yao, Mingfa and Jia, Ming and Reitz, Rolf D.},
abstractNote = {},
doi = {10.1021/ef500867p},
journal = {Energy and Fuels},
number = 8,
volume = 28,
place = {United States},
year = {Fri Jul 11 00:00:00 EDT 2014},
month = {Fri Jul 11 00:00:00 EDT 2014}
}
  • The secondary to 1000 deg F. -deuterium isotope effects were measured in the water solvolytic reaction of alkyl halides and sulfonated for primary, secondary, and tertiary species. In (k/sub H//k/sub D/) 1). This isotope effect may be associated with varying degrees of hyperconjugation or altered nonbonding intramolecular forces. The experiments make it difficult to decide which effect is most important.
  • A study was carried out on carbon deposition on the surface of 5% KCl/SiO/sub 2/ upon the decomposition of di-tert-butyl peroxide, (DTBP). The EPR spectra of the paramagnetic sites in the carbon deposit depend on the amount of peroxide decomposed. The EPR spectrum of the RO/sub 2/ radicals stabilized on KCl crystals was recorded. Carbonization of the surface as a result of the decomposition of DTBP is responsible for the chemical reactions, including the reactions of adsorbed RO/sub 2/ radicals, the formation of carbon deposits with strongly delocalized electrons in the conductance band, and the reaction of the radicals withmore » localized paramagnetic sites, which should hinder the removal of the radicals from the surface into the gas phase.« less
  • Energy transfer from a variety of aromatic hydrocarbons and ketones to di-tert-butyl peroxide has been examined by using nanosecond laser flash photolysis techniques. Triplet energy transfer to the peroxide leads to its efficient cleavage into two tert-butoxy radicals. Representative rate constants for triplet quenching in benzene at 25/sup 0/C are 7.9 x 10/sup 6/, 3.4 x 10/sup 6/, and 7.0 x 10/sup 4/M/sup -1/s/sup -1/ for p-methoxypropiophenone, benzophenone, and benz(a)anthracene, respectively. The rate of transfer for p-methoxypropiophenone (E/sub T/ = 72.5 kcal/mol) is approximately temperature independent; for lower energy sensitizers ca. 0.17 kcal/mol activation energy is required for each kilocaloriemore » per mole decrease in triplet energy. No evidence indicating exciplex intermediacy was found. A model for energy transfer to a repulsive state of the peroxide is proposed in which no activation energy is required if the sensitizer meets the energy requirements at the 0-0 equilibrium distance. For sensitizers of lower triplet energy, energy transfer to a repulsive state is proposed to occur from a thermally activated ground state having a greater than equilibrium oxygen-oxygen bond length. The same mechanism may apply in other systems where the acceptor lacks low-lying excited states. A few rate constants for the quenching of singlet sensitizers have also been determined by using fluorescence techniques.« less