Catalytic oxidation. IV. Ethylene and propylene oxidation over gold

Noel W. Cant, W. Keith Hall

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The heterogeneous oxidation of C 2H 4 and C 3H 6 was studied over several gold catalysts. The principal products from C 2H 4 were CO 2 and H 2O, but small amounts of acetic acid and acetaldehyde were also found. In addition to these products, up to 3% acetone and 50% acrolein were obtained from C 3H 6. Gold sponge and Au/SiO 2 were much more selective for acrolein formation than Au/α-Al 2O 3. For both olefins, the rate of total oxidation was first order in oxygen pressure and zero order in olefin pressure at low pressures. The apparent activation energies (except for C 2H 4 over Au sponge) ranged from 17 to 22 kcal mol -1. Acrolein formation had a much lower apparent activation energy (9-12 kcal mol -1), was also first order in O 2, but showed a maximum rate for C 3H 6 pressures near 30 Torr. Oxidation of propylene-1- 13C produced acrolein molecules in which the 13C was equally distributed between the end positions. Similarly, CD 3CHCH 2 and CH 3CHCD 2 both yielded CH 2CHCDO and CD 2CHCHO in about equal amounts, although the rate of the reaction with the former olefin was only about 40% that of the latter or that of CH 3CHCH 2. These results indicated that the rate-determining step in acrolein formation was abstraction of a methyl hydrogen (or deuterium) to yield a symmetrical allylic intermediate. The modes of fragmentation of acrolein during mass spectral analysis are discussed on the basis of high-resolution measurements of the labeled acroleins formed in the present work.

LanguageEnglish
Pages2914-2921
Number of pages8
JournalJournal of Physical Chemistry
Volume75
Issue number19
Publication statusPublished - 1971

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Acrolein
Catalytic oxidation
propylene
Gold
Propylene
Ethylene
ethylene
gold
alkenes
Olefins
Oxidation
oxidation
Alkenes
methylidyne
acroleins
Activation energy
activation energy
Acetaldehyde
acetaldehyde
products

Cite this

Cant, Noel W. ; Hall, W. Keith. / Catalytic oxidation. IV. Ethylene and propylene oxidation over gold. In: Journal of Physical Chemistry. 1971 ; Vol. 75, No. 19. pp. 2914-2921.
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abstract = "The heterogeneous oxidation of C 2H 4 and C 3H 6 was studied over several gold catalysts. The principal products from C 2H 4 were CO 2 and H 2O, but small amounts of acetic acid and acetaldehyde were also found. In addition to these products, up to 3{\%} acetone and 50{\%} acrolein were obtained from C 3H 6. Gold sponge and Au/SiO 2 were much more selective for acrolein formation than Au/α-Al 2O 3. For both olefins, the rate of total oxidation was first order in oxygen pressure and zero order in olefin pressure at low pressures. The apparent activation energies (except for C 2H 4 over Au sponge) ranged from 17 to 22 kcal mol -1. Acrolein formation had a much lower apparent activation energy (9-12 kcal mol -1), was also first order in O 2, but showed a maximum rate for C 3H 6 pressures near 30 Torr. Oxidation of propylene-1- 13C produced acrolein molecules in which the 13C was equally distributed between the end positions. Similarly, CD 3CHCH 2 and CH 3CHCD 2 both yielded CH 2CHCDO and CD 2CHCHO in about equal amounts, although the rate of the reaction with the former olefin was only about 40{\%} that of the latter or that of CH 3CHCH 2. These results indicated that the rate-determining step in acrolein formation was abstraction of a methyl hydrogen (or deuterium) to yield a symmetrical allylic intermediate. The modes of fragmentation of acrolein during mass spectral analysis are discussed on the basis of high-resolution measurements of the labeled acroleins formed in the present work.",
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Catalytic oxidation. IV. Ethylene and propylene oxidation over gold. / Cant, Noel W.; Hall, W. Keith.

In: Journal of Physical Chemistry, Vol. 75, No. 19, 1971, p. 2914-2921.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Catalytic oxidation. IV. Ethylene and propylene oxidation over gold

AU - Cant, Noel W.

AU - Hall, W. Keith

PY - 1971

Y1 - 1971

N2 - The heterogeneous oxidation of C 2H 4 and C 3H 6 was studied over several gold catalysts. The principal products from C 2H 4 were CO 2 and H 2O, but small amounts of acetic acid and acetaldehyde were also found. In addition to these products, up to 3% acetone and 50% acrolein were obtained from C 3H 6. Gold sponge and Au/SiO 2 were much more selective for acrolein formation than Au/α-Al 2O 3. For both olefins, the rate of total oxidation was first order in oxygen pressure and zero order in olefin pressure at low pressures. The apparent activation energies (except for C 2H 4 over Au sponge) ranged from 17 to 22 kcal mol -1. Acrolein formation had a much lower apparent activation energy (9-12 kcal mol -1), was also first order in O 2, but showed a maximum rate for C 3H 6 pressures near 30 Torr. Oxidation of propylene-1- 13C produced acrolein molecules in which the 13C was equally distributed between the end positions. Similarly, CD 3CHCH 2 and CH 3CHCD 2 both yielded CH 2CHCDO and CD 2CHCHO in about equal amounts, although the rate of the reaction with the former olefin was only about 40% that of the latter or that of CH 3CHCH 2. These results indicated that the rate-determining step in acrolein formation was abstraction of a methyl hydrogen (or deuterium) to yield a symmetrical allylic intermediate. The modes of fragmentation of acrolein during mass spectral analysis are discussed on the basis of high-resolution measurements of the labeled acroleins formed in the present work.

AB - The heterogeneous oxidation of C 2H 4 and C 3H 6 was studied over several gold catalysts. The principal products from C 2H 4 were CO 2 and H 2O, but small amounts of acetic acid and acetaldehyde were also found. In addition to these products, up to 3% acetone and 50% acrolein were obtained from C 3H 6. Gold sponge and Au/SiO 2 were much more selective for acrolein formation than Au/α-Al 2O 3. For both olefins, the rate of total oxidation was first order in oxygen pressure and zero order in olefin pressure at low pressures. The apparent activation energies (except for C 2H 4 over Au sponge) ranged from 17 to 22 kcal mol -1. Acrolein formation had a much lower apparent activation energy (9-12 kcal mol -1), was also first order in O 2, but showed a maximum rate for C 3H 6 pressures near 30 Torr. Oxidation of propylene-1- 13C produced acrolein molecules in which the 13C was equally distributed between the end positions. Similarly, CD 3CHCH 2 and CH 3CHCD 2 both yielded CH 2CHCDO and CD 2CHCHO in about equal amounts, although the rate of the reaction with the former olefin was only about 40% that of the latter or that of CH 3CHCH 2. These results indicated that the rate-determining step in acrolein formation was abstraction of a methyl hydrogen (or deuterium) to yield a symmetrical allylic intermediate. The modes of fragmentation of acrolein during mass spectral analysis are discussed on the basis of high-resolution measurements of the labeled acroleins formed in the present work.

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