261. The kinetics of chlorohydrin formation. Part II. The reaction between hypochlorous acid and allyl alcohol in the presence of sodium acetate–acetic acid buffers of constant ph

1950 ◽  
Vol 0 (0) ◽  
pp. 1286-1289 ◽  
Author(s):  
G. C. Israel
Keyword(s):  
Acetic Acid ◽  
Allyl Alcohol ◽  
Sodium Acetate ◽  
Hypochlorous Acid ◽  
Constant Ph ◽  
Kinetics Of

Equilibria between Palladium(II) Acetate and Olefins in Acetic Acid containing Sodium Acetate

1975 ◽  
Vol 53 (12) ◽  
pp. 1833-1841 ◽  
Author(s):  
Raj N. Pandey ◽  
Patrick M. Henry
Keyword(s):  
Acetic Acid ◽  
Sodium Acetate ◽  
Solution Composition ◽  
Kinetics Of Oxidation ◽  
Complex Equilibria ◽  
Π Complex ◽  
Allylic Esters ◽  
Kinetics Of

π-Complex equilibria between dimeric Pd(II) acetate and various olefins (ethylene, styrene, 3,3-dimethyl-1-butene, vinylic and allylic esters) in acetic acid solvent have been investigated by spectral means. The results indicate two π-complexes are formed. The first π-complex, which is formed rapidly, is a dimeric π-complex (ol = olefin ).[Formula: see text]The Benesi–Hildebrand plots for these complexes are linear for all olefins and thus values of Kπ22 can be readily evaluated. The values of the equilibrium coefficient, Kπ22, do not change with solution composition or [NaOAc]. The second π-complex is formed slowly. The data are consistent only with the equilibrium[Formula: see text]The data are inconsistent with the equilibrium[Formula: see text]which is analogous to that reported for the Na2Pd2Cl6 reaction with olefins in acetic acid. Furthermore, previous assumptions as to the equilibria between ethylene and Pd(II) in the all-acetate system have proved incorrect, and so the kinetics of oxidation of ethylene in this system must be reinterpreted in view of the present results.

scholarly journals Kinetics of Oxidation of Some Amino Acids by N-Chlorosaccharin in Aqueous Acetic Acid Medium

2004 ◽  
Vol 1 (2) ◽  
pp. 127-131 ◽  
Author(s):  
N. A. Mohamed Farook ◽  
R. Prabaharan ◽  
S. Rahini ◽  
R. Senthil Kumar ◽  
G. Rajamahendran ◽  
...  
Keyword(s):  
Amino Acids ◽  
Acetic Acid ◽  
Acid Medium ◽  
Hypochlorous Acid ◽  
Activation Parameters ◽  
Slow Step ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
Kinetics Of Oxidation ◽  
Kinetics Of

The kinetics of oxidation of some amino acids namely, glycine, alanine, aspartic acid, arginine, and histidine, (AA) byN-chlorosaccharin (NCSA) in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order in [AA], [NCSA] and of inverse fractional order in [H+]. The main product of the oxidation is the corresponding aldehyde. The ionic strength on the reaction rate has no significant effect. The effect of changing the dielectric constant of the medium on the rate indicates the reaction to be of dipole-dipole type. Hypochlorous acid has been postulated as the reactive oxidizing species. The reaction constants involved in the mechanism are derived. The activation parameters are computed with respect to slow step of the mechanism.

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).

scholarly journals Kinetics of Oxidation of Some Essential Amino Acids by N-Chlorosaccharin in Aqueous Acetic Acid Medium

2004 ◽  
Vol 1 (2) ◽  
pp. 132-136 ◽  
Author(s):  
N. A. Mohamed Farook ◽  
G. A. Seyed Dameem ◽  
A. Murugesan ◽  
M. Kanagaraj
Keyword(s):  
Amino Acids ◽  
Acetic Acid ◽  
Acid Medium ◽  
Hypochlorous Acid ◽  
Essential Amino Acids ◽  
Slow Step ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
Kinetics Of Oxidation ◽  
Kinetics Of

The kinetics of oxidation of some essential amino acids namely, valine, leucine and phenylalanine, (AA) byN-chlorosaccharin (NCSA) in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order in [AA], [NCSA] and of inverse fractional order in [H+]. The main product of the oxidation is the corresponding aldehyde. The ionic strength on the reaction rate has no significant effect. The effect of changing the dielectric constant of the medium on the rate indicates the reaction to be of dipole-dipole type. Hypochlorous acid has been postulated as the reactive oxidizing species. The reaction constants involved in the mechanism are derived. The activation parameters are computed with respect to slow step of the mechanism

Sign in / Sign up

Export Citation Format

Share Document