jp0602878_si_001.pdf (764.59 kB)
Thermodynamic Properties (Enthalpy, Bond Energy, Entropy, and Heat Capacity) and Internal Rotor Potentials of Vinyl Alcohol, Methyl Vinyl Ether, and Their Corresponding Radicals
journal contribution
posted on 2006-06-29, 00:00 authored by Gabriel da Silva, Chol-Han Kim, Joseph W. BozzelliVinyl alcohols (enols) have been discovered as important intermediates and products in the oxidation and
combustion of hydrocarbons, while methyl vinyl ethers are also thought to occur as important combustion
intermediates. Vinyl alcohol has been detected in interstellar media, while poly(vinyl alcohol) and poly(methyl vinyl ether) are common polymers. The thermochemical property data on these vinyl alcohols and
methyl vinyl ethers is important for understanding their stability, reaction paths, and kinetics in atmospheric
and thermal hydrocarbon−oxygen systems. Enthalpies
, entropies
, and heat capacities (Cp(T))
are determined for CH2CHOH, C•HCHOH, CH2C•OH, CH2CHOCH3, C•HCHOCH3, CH2C•OCH3,
and CH2CHOC•H2. Molecular structures, vibrational frequencies,
, and Cp(T) are calculated at the
B3LYP/6-31G(d,p) density functional calculation level. Enthalpies are also determined using the composite
CBS-Q, CBS-APNO, and G3 methods using isodesmic work reactions to minimize calculation errors. Potential
barriers for internal rotors are calculated at the B3LYP/6-31G(d,p) level and used to determine the hindered
internal rotational contributions to entropy and heat capacity. The recommended ideal gas phase
values calculated in this study are the following (in kcal mol-1): −30.0, −28.9 (syn, anti) for CH2CHOH;
−25.6, −23.9 for CH2CHOCH3; 31.3, 33.5 for C•HCHOH; 27.1 for anti-CH2C•OH; 35.6, 39.3 for
C•HCHOCH3; 33.5, 32.2 for CH2C•OCH3; 21.3, 22.0 for CH2CHOC•H2. Bond dissociation energies
(BDEs) and group additivity contributions are also determined. The BDEs reveal that the O−H, O−CH3,
C−OH, and C−OCH3 bonds in vinyl alcohol and methyl vinyl ether are similar in energy to those in the
aromatic molecules phenol and methyl phenyl ether, being on average around 3 kcal mol-1 weaker in the
vinyl systems. The keto−enol tautomerization enthalpy for the interconversion of vinyl alcohol to acetaldehyde
is determined to be −9.7 kcal mol-1, while the activation energy for this reaction is calculated as 55.9 kcal
mol-1; this is the simplest keto−enol tautomerization and is thought to be important in the reactions of vinyl
alcohol. Formation of the formyl methyl radical (vinoxy radical/vinyloxy radical) from both vinyl alcohol
and methyl vinyl ether is also shown to be important, and its reactions are discussed briefly.