TY - JOUR
T1 - Does H4SO5 exist?
AU - Murillo, Fernando
AU - Vargas-Caamal, Alba
AU - Pan, Sudip
AU - Cabellos, José Luis
AU - Mora-Fonz, Miguel J.
AU - Muñoz-Castro, Alvaro
AU - Restrepo, Albeiro
AU - Merino, Gabriel
N1 - Publisher Copyright:
© 2017 the Owner Societies.
PY - 2017
Y1 - 2017
N2 - The possible existence of H4SO5 in aqueous sulfuric acid is analyzed in detail. For bare H4SO5, the computed free energy barrier for the exergonic transformation of H4SO5 into the H2SO4⋯H2O complex is only 3.8 kcal mol-1. The presence of water or sulfuric acid catalyzes the dehydration to such an extent that it becomes almost a barrierless process. In the gas phase, dehydration of H4SO5 is an autocatalytic reaction as the water molecule produced by the decomposition of one H4SO5 molecule induces further dissociation. Thus, in solution, the surrounding water molecules make the para-sulfuric acid a very vulnerable species to exist. The simulated Raman spectra also corroborate the absence of H4SO5 in solution.
AB - The possible existence of H4SO5 in aqueous sulfuric acid is analyzed in detail. For bare H4SO5, the computed free energy barrier for the exergonic transformation of H4SO5 into the H2SO4⋯H2O complex is only 3.8 kcal mol-1. The presence of water or sulfuric acid catalyzes the dehydration to such an extent that it becomes almost a barrierless process. In the gas phase, dehydration of H4SO5 is an autocatalytic reaction as the water molecule produced by the decomposition of one H4SO5 molecule induces further dissociation. Thus, in solution, the surrounding water molecules make the para-sulfuric acid a very vulnerable species to exist. The simulated Raman spectra also corroborate the absence of H4SO5 in solution.
UR - http://www.scopus.com/inward/record.url?scp=85024473750&partnerID=8YFLogxK
U2 - 10.1039/c7cp01328k
DO - 10.1039/c7cp01328k
M3 - Artículo
C2 - 28636012
AN - SCOPUS:85024473750
SN - 1463-9076
VL - 19
SP - 17088
EP - 17093
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 26
ER -