Kinetics of the acid-catalyzed isomerization of phenylbutenes in glacial acetic acid

1972 ◽  
Vol 94 (4) ◽  
pp. 1247-1249 ◽  
Author(s):  
R. S. Schwartz ◽  
H. Yokokawa ◽  
E. W. Graham
Keyword(s):  
Acetic Acid ◽  
Glacial Acetic Acid ◽  
Acid Catalyzed ◽  
Kinetics Of

Kinetics of metalloporphyrin formation in glacial acetic acid

1970 ◽  
Vol 9 (9) ◽  
pp. 2034-2037 ◽  
Author(s):  
D. James Kingham ◽  
Doreen A. Brisbin
Keyword(s):  
Acetic Acid ◽  
Glacial Acetic Acid ◽  
Kinetics Of

scholarly journals Kinetic studies of metalloporphyrin formation. Part I. Mn(II) with hematoporphyrin

1968 ◽  
Vol 46 (22) ◽  
pp. 3431-3436 ◽  
Author(s):  
Doreen A. Brisbin ◽  
Robert J. Balahura
Keyword(s):  
Acetic Acid ◽  
Glacial Acetic Acid ◽  
Kinetic Studies ◽  
Activation Energies ◽  
Kinetics Of

The kinetics of the formation of Mn(III) hematoporphyrin in glacial acetic acid has been studied spectrophotometrically.On addition of Mn(II) to porphyrin in glacial acetic acid a species which appears to be the monocation immediately is formed and is then converted to Mn(III) hematoporphyrin at a rate suitable for kinetic studies.The rates of reaction were measured at 45, 50, and 55 °C and the activation energies were calculated.

Palladium(II) Catalyzed Exchange Reactions. XI. Vinyl Propionate Exchange with Acetic Acid Catalyzed by Palladium(II) Acetate

1975 ◽  
Vol 53 (15) ◽  
pp. 2223-2231 ◽  
Author(s):  
Raj N. Pandey ◽  
Patrick M. Henry
Keyword(s):  
Acetic Acid ◽  
Sodium Acetate ◽  
Exchange Reactions ◽  
Free System ◽  
Acetate Concentration ◽  
Rate Expression ◽  
Π Complex ◽  
Acid Catalyzed ◽  
Kinetics Of ◽  
Vinyl Propionate

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).

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

2013 ◽  
Vol 111 (1) ◽  
pp. 15-27 ◽  
Author(s):  
Xiufeng Lu ◽  
Hengbo Yin ◽  
Lingqin Shen ◽  
Yonghai Feng ◽  
Aili Wang ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Reaction Kinetics ◽  
Esterification Reaction ◽  
Keggin Heteropolyacids ◽  
Acid Catalyzed ◽  
Kinetics Of

Influence of the acidity on the kinetics of diphenylamine oxidation by peroxodisulfate anions

1993 ◽  
Vol 71 (2) ◽  
pp. 167-174 ◽  
Author(s):  
M. Balón ◽  
P. Guardado ◽  
C. Carmona ◽  
J. Hidalgo ◽  
M. A. Munoz
Keyword(s):  
Acetic Acid ◽  
Decomposition Products ◽  
Kinetic Rate ◽  
Rate Law ◽  
Rate Determining Step ◽  
Water Media ◽  
Acid Catalyzed ◽  
Radical Traps ◽  
Kinetics Of ◽  
Acetic Acid Acetate

A kinetic study is reported on the oxidation of diphenylamine (DPA) by peroxodisulfate (PDS) anions in H2SO4 and buffered acetic acid – acetate 20% v/v methanol–water media. The primary detectable product of the reaction is N-phenyl-p-benzoquinoneimine (PBQ), which undergoes acid-catalyzed hydrolysis giving different decomposition products. At pH > 4 (acetic acid – acetate buffers) the hydrolytic decomposition is very slow and it does not interfere with PBQ formation, but in H2SO4 media of pH < 2.5, PBQ decomposes as it is formed. In these media, the reaction obeys the kinetic rate law:[Formula: see text]a, the kinetic parameter, being acid dependent. Neither radical promoters (Ag+) nor radical traps (allyl alcohol) influence the reaction rate. In acetic acid – acetate buffers of pH > 4 the kinetic rate law is simple: first order in each one of the reactants, and acid independent. These results have been interpreted by assuming the formation, in a preequilibrium step, of an N-diphenylhydroxylamine-O-sulfonate intermediate, which further rearranges to yield PBQ. The rate-determining step of the reaction changes with the protonation state of the intermediate, whose protonation pKa has been kinetically estimated as 2.4.

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