The catalyzed dehydration of acetaldehyde hydrate, and the effect of structure on the velocity of protolytic reactions
10.1098/rspa.1949.0055
Crossref journal-article
The Royal Society
Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences (175)
Abstract

The reaction CH 3 CH(OH) 2 →CH 3 CHO + H 2 O has been studied kinetically in aqueous acetone using a dilatometric method. It was found to be a first-order reaction, catalyzed by uncharged acids, cation acids, uncharged bases and anion bases. Quantitative measurements were made on the catalytic effect of 63 acids. The results for 32 carboxylic acids and 15 phenols conform approximately to a single relation between catalytic power and dissociation constant in water, but most of the 16 acids of other types show considerable positive or negative deviations from this relation. These deviations are related to the structures of the catalysts, and it is shown that, for acids of equal strength, the velocity of protolytic change is decreased by a mesomeric charge-shift in the anion, and is increased if mesomerism in the acid is lost on ionization. This principle is related to the occurrence of pseudo-acids and bases, and is interpreted in terms of molecular potential energy curves.

Bibliography

The catalyzed dehydration of acetaldehyde hydrate, and the effect of structure on the velocity of protolytic reactions. (1949). Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 197(1049), 141–159.

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Dates
Type When
Created 18 years, 8 months ago (Dec. 15, 2006, 4:53 p.m.)
Deposited 4 years, 6 months ago (Feb. 18, 2021, 4:54 p.m.)
Indexed 2 months ago (July 2, 2025, 1:30 p.m.)
Issued 76 years, 3 months ago (June 7, 1949)
Published 76 years, 3 months ago (June 7, 1949)
Published Online 28 years, 8 months ago (Jan. 1, 1997)
Published Print 76 years, 3 months ago (June 7, 1949)
Funders 0

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@article{1949, and the effect of structure on the velocity of protolytic reactions_1949, volume={197}, ISSN={2053-9169}, url={http://dx.doi.org/10.1098/rspa.1949.0055}, DOI={10.1098/rspa.1949.0055}, number={1049}, journal={Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences}, publisher={The Royal Society}, year={1949}, month=jun, pages={141–159} }