Document Detail

Photoinduced reactivity of liquid ethanol at high pressure.
MedLine Citation:
PMID:  21053928     Owner:  NLM     Status:  In-Process    
The room temperature photoinduced reactivity of liquid ethanol has been studied as a function of pressure up to 1.5 GPa by means of a diamond anvil cell. Exploiting the dissociative character of the lowest electronic excited states, reached through two-photon absorption of near-UV photons (350 nm), irreversible reactive processes have been triggered in the pure system. The active species are radicals forming along two main dissociation channels involving the split of C-O and O-H bonds. The characterization of the reaction products has been performed by in situ FTIR and Raman spectroscopy. At pressures of a few megapascals, molecular hydrogen is the main reaction product, an important issue in the framework of environmentally friendly synthesis of this energetic vector. In the gigapascal range, the main products are ethane, 2-butanol, 2,3-butanediol, 1,1-diethoxyethane, and some carbonylic compounds. The relative amount of these species changes with pressure reflecting the nature of the radicals formed in the photodissociation process. As the pressure increases, the processes requiring a greater molecularity are favored, whereas those requiring internal rearrangements are inhibited. Disproportion products like CH(4), H(2)O, and CO(2) increase when the amount of ethanol decreases due to the reaction, becoming the main products only when ethanol is exhausted.
Matteo Ceppatelli; Samuele Fanetti; Margherita Citroni; Roberto Bini
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Publication Detail:
Type:  Journal Article     Date:  2010-11-05
Journal Detail:
Title:  The journal of physical chemistry. B     Volume:  114     ISSN:  1520-5207     ISO Abbreviation:  J Phys Chem B     Publication Date:  2010 Dec 
Date Detail:
Created Date:  2010-11-25     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101157530     Medline TA:  J Phys Chem B     Country:  United States    
Other Details:
Languages:  eng     Pagination:  15437-44     Citation Subset:  -    
LENS, European Laboratory for Nonlinear Spectroscopy, Via N. Carrara 1, I-50019 Sesto Fiorentino, Firenze, Italy.
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