Reaction kinetics of the esterification reaction between ethanol and acetic acid catalyzed by Keggin heteropolyacids

The kinetics of the palladium(II) acetate catalyzed exchange of vinyl propionate with acetic acid solvent to give vinyl acetate has been studied in the sodium acetate concentration range from 0 to 1 M. The exchange rate first sharply increases as [NaOAc] increases, reaches a maximum at about 0.2 M and then gradually decreases as the sodium acetate concentration is in-creased to 1.0 M. Using previous results on the equilibrium between palladium(II) acetate and sodium acetate in acetic acid it can be shown that the rate expression for exchange is: rate = (ko + kt[Pd3(OAc)6] + kd[Na2Pd2(OAc)6]) [CH2=CHO2CC2H5] where ko = 2 × 10−4 s−1, kt = 0.045 M−1 s−1, and kd = 0.089 M−1 s−1. A monomeric palladium(II) species, Na2Pd(OAc)4, formed at high [NaOAc] is unreactive. Since the rate expression does not contain a term in [NaOAc], the sodium acetate serves only to convert one palladium(II) species to another. The lack of a [NaOAc] term in the rate expression for the Na2Pd2(OAc)6 catalyzed reaction is believed to result from cancellation of an inhibitory term for π-complex formation by a catalytic term in [NaOAc] in the rate determining conversion of π -complex to σ-complex (acetoxypalladation). Stereochemical studies indicate that acetoxypalladation is nonstereospecific. This result is expected since in the chloride free system acetate is both a ligand and a reactant. Thus it can attack from both inside and outside the coordination sphere of Pd(II).

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Reaction kinetics of ethane partial oxidation to acetic acid

Applied Petrochemical Research ◽

10.1007/s13203-018-0195-8 ◽

2018 ◽

Vol 8 (1) ◽

pp. 29-38 ◽

Cited By ~ 1

Author(s):

Sulaiman I. Al-Mayman ◽

Moustafa A. Soliman ◽

Abdulrahman S. Al-Awadi ◽

Yousef S. Al-Zeghayer

Keyword(s):

Acetic Acid ◽

Reaction Kinetics ◽

Partial Oxidation ◽

Kinetics Of

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Reaction Kinetics of the Homogeneously Catalyzed Esterification of 1-Butanol with Acetic Acid in a Wide Range of Initial Compositions

Industrial & Engineering Chemistry Research ◽

10.1021/ie050789s ◽

2006 ◽

Vol 45 (6) ◽

pp. 1869-1874 ◽

Cited By ~ 21

Author(s):

Sascha Grob ◽

Hans Hasse

Keyword(s):

Acetic Acid ◽

Reaction Kinetics ◽

Wide Range ◽

Kinetics Of

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Autocatalyzed and heterogeneously catalysed esterification kinetics of glycolic acid with ethanol

Reaction Chemistry & Engineering ◽

10.1039/d1re00418b ◽

2021 ◽

Author(s):

Laura Reyes ◽

Clémence Nikitine ◽

Léa Vilcocq ◽

Pascal Fongarland

Keyword(s):

Reaction Kinetics ◽

Chemical Equilibrium ◽

Glycolic Acid ◽

Esterification Reaction ◽

Kinetics Of

The chemical equilibrium and reaction kinetics in homogeneously and heterogeneously catalyzed systems were investigated for the reversible esterification reaction of glycolic acid with ethanol. In a first approach, the thermodynamic...

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