Analyses of reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems using recently developed thermodynamic rate equations

2019 ◽  
Vol 52 (1) ◽  
pp. 52-60 ◽  
Author(s):  
F. L. Wiseman ◽  
D. W. Scott ◽  
J. Tamine ◽  
R. O'Connell ◽  
A. Smarra ◽  
...  
Keyword(s):  
Acetic Anhydride ◽  
Reaction Rate ◽  
Rate Equations ◽  
Rate Data ◽  
Acetone Water ◽  
Hydrolysis Of

PRESSURE EFFECT AND MECHANISM IN ACID CATALYSIS: V. THE HYDROLYSIS OF ACETIC ANHYDRIDE

1959 ◽  
Vol 37 (8) ◽  
pp. 1360-1366 ◽  
Author(s):  
J. Koskikallio ◽  
D. Pouli ◽  
E. Whalley
Keyword(s):  
Acetic Anhydride ◽  
Acid Catalysis ◽  
Pressure Effect ◽  
Valid Method ◽  
Acetone Water ◽  
Entropy Of Activation ◽  
Acid Catalyzed ◽  
Hydrolysis Of

The spontaneous and the acid-catalyzed hydrolyses of acetic anhydride have been measured as a function of temperature over the range 0 to 40 °C, as a function of pressure over the range 0 to 3 kb at 0 °C, and as a function of solvent over the range 0 to 70.3% w/w acetone–water at 0 °C. The results are discussed with reference to the mechanisms of the hydrolyses. The volume and entropy of activation of the acid-catalyzed hydrolysis are −17.1 ± ~1.3 cm3 mole−1 and ~ −20 cal deg−1 mole−1, showing that the mechanism[Formula: see text]suggested because the rate was proportional to Hammett's h0, is not correct. It follows that the Zucker–Hammett hypothesis is invalid for this reaction, as we have shown previously for other reactions, and hence that it does not provide a valid method of distinguishing between the A-1 and A-2 mechanisms.

scholarly journals Kinetics of the Hydrolysis of Acetic Anhydride in Acetone-Water and Dioxane-Water Mixtures.

1960 ◽  
Vol 14 ◽  
pp. 1343-1348 ◽  
Author(s):  
Jouko Koskikallio ◽  
H. Flood ◽  
S. Rundqvist ◽  
E. Varde ◽  
Gertrud Westin
Keyword(s):  
Acetic Anhydride ◽  
Acetone Water ◽  
Kinetics Of ◽  
Hydrolysis Of

Upgrading to nutrient removal by means of internal carbon from sludge hydrolysis

1994 ◽  
Vol 29 (12) ◽  
pp. 31-40 ◽  
Author(s):  
Pia Prohaska Brinch ◽  
Kim Rindel ◽  
Kathryn Kalb
Keyword(s):  
Reaction Rate ◽  
Wastewater Treatment Plants ◽  
Secondary Treatment ◽  
N Removal ◽  
Sludge Hydrolysis ◽  
Speed Up ◽  
On Line ◽  
Full Scale Tests ◽  
Biological Phosphorus ◽  
Hydrolysis Of

Due to the introduction of stricter nutrient effluent standards, many existing wastewater treatment plants performing only primary or secondary treatment are about to be upgraded. As the space available at the plants is, however, often limited, processes are required which will accommodate the need for increased treatment capacity without requiring much more space. In the hydrolysis of primary or pre-precipitated sludge direct-degradable organic carbon is produced which can speed up the reaction rate and increase both biological phosphorus and nitrogen removal. Full-scale tests with dosing of hydrolysate for biological P and N removal, respectively, have shown that this is a most viable process. The use of on-line monitoring has improved the process further.

Synthesis of conjugates of 1-(carboxymethyl)cytosine and 1-(5-O-carboxymethyl-β-D-arabinofuranosyl)cytosine with proteins

1979 ◽  
Vol 44 (10) ◽  
pp. 3023-3032 ◽  
Author(s):  
Helmut Pischel ◽  
Antonín Holý ◽  
Günther Wagner
Keyword(s):  
Human Serum Albumin ◽  
Acetic Anhydride ◽  
Serum Albumin ◽  
Human Serum ◽  
Activated Esters ◽  
Hydrolysis Of

1-(Carboxymethyl)cytosine (Ia), 1-(5-O-carboxymethyl-β-D-arabinofuranosyl)cytosine (IIa) and 5'-O-carboxylmethylcytidine (IIIa) were transformed by treatment with acetic anhydride and 4-dimethylaminopyridine to the peracetyl derivatives Ib-IIIb. These products reacted with p-nitrophenol in the presence of N, N'-dicyclohexylcarbodiimide to give the activated esters Ic-IIIc which on reaction with ammonia, dimethylamine or 2-aminoethanol afforded the corresponding carboxamides Id-IIId, IIe,f. Reactions of Ic and IIc with human serum albumin and bovine γ-globulin at pH 9.2, followed by hydrolysis of the N- or O-acetyl groups at pH 9.5, gave 50% up to 64% yields of the respective conjugates Ig, IIg and Ih, IIh.

Cyclization and acid-catalyzed hydrolysis of O-benzoylbenzamidoximes

1986 ◽  
Vol 51 (12) ◽  
pp. 2786-2797
Author(s):  
František Grambal ◽  
Jan Lasovský
Keyword(s):  
Reaction Rate ◽  
Kinetic Isotope ◽  
Acid Base Equilibrium ◽  
Mineral Acids ◽  
Kinetics Of Formation ◽  
Acid Catalyzed ◽  
Ph Scale ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Derivatives Of

Kinetics of formation of 1,2,4-oxadiazoles from 24 substitution derivatives of O-benzoylbenzamidoxime have been studied in sulphuric acid and aqueous ethanol media. It has been found that this medium requires introduction of the Hammett H0 function instead of the pH scale beginning as low as from 0.1% solutions of mineral acids. Effects of the acid concentration, ionic strength, and temperature on the reaction rate and on the kinetic isotope effect have been followed. From these dependences and from polar effects of substituents it was concluded that along with the cyclization to 1,2,4-oxadiazoles there proceeds hydrolysis to benzamidoxime and benzoic acid. The reaction is thermodynamically controlled by the acid-base equilibrium of the O-benzylated benzamidoximes.

Chemistry of Fenchonesulfonic Acid Derivatives

1995 ◽  
Vol 50 (2) ◽  
pp. 283-288 ◽  
Author(s):  
Gabriele Wagner ◽  
Uwe Verfürth ◽  
Rudolf Herrmann
Keyword(s):  
Acetic Anhydride ◽  
Thionyl Chloride ◽  
Sulfonic Acid ◽  
Reaction Rate ◽  
Enantiomeric Excess ◽  
Methyl Group ◽  
Close Analogy ◽  
Chiral Sulfoxides ◽  
Mndo Calculations ◽  
Nmr Techniques

(1 S) - (+)-Fenchone is sulfonated by SO3 or H2SO4/acetic anhydride in the bridgehead methyl group. This could be confirmed by NMR techniques (INADEQUATE). The fenchonesulfonic acid obtained is converted (SOCl2/NH3) to the cyclic fenchonesulfonimide, which can be oxidized to the corresponding oxaziridine, in close analogy to 10-camphorsulfonimide. Improved procedures for this reaction sequences are given. During the treatment of the sulfonic acid with thionyl chloride, a byproduct with a rearranged bicyclic skeleton is observed whose structure has been determined by ozonolytic degradation and NMR techniques. A possible mechanism for this rearrangement is suggested, based on MNDO calculations of the intermediate carbocations. The fenchonesulfonyloxaziridine oxidizes sulfides to chiral sulfoxides with appreciable enantiomeric excess, but very low reaction rate. A comparison with camphor-derived oxaziridines having similar steric requirements is made.

Potentiodynamic examination of electrode kinetics for electroactive adsorbed species: applications to the reduction of noble metal surface oxides

1969 ◽  
Vol 310 (1503) ◽  
pp. 541-563 ◽  
Keyword(s):  
Noble Metals ◽  
Reaction Rate ◽  
Substrate Surface ◽  
Intrinsic Property ◽  
Surface Heterogeneity ◽  
Surface Oxide ◽  
Rate Equations ◽  
Quasi Equilibrium ◽  
Linear Potential ◽  
Reaction Velocity

The relation between reaction rate and potential (or time) for electrochemical surface processes occurring under potentiodynamic control (linear potential-time programme) has been investigated with particular reference to the behaviour of thin surface oxide films on noble metals. The kinetics of processes involving adsorbed electroactive species are treated for several model cases; the rate equations are developed for mechanisms involving various reaction orders or for processes involving adsorbed reactant interactions and surface heterogeneity effects. By examination of the dependence of the reaction rate (current) with time and the effect of potential scan rate, v , on the maximum reaction velocity and the potential at which it occurs, the models may be distinguished. In this manner, the inter­dependence of v and the reaction velocity constants k a and k c for the anodic oxidation and the cathodic reduction processes respectively, can be quantitatively established. The relation between quasi-equilibrium situations where the reverse reaction is significant and irreversible situations where it is not can be demonstrated. Heterogeneity terms introduced into the kinetic relations express deviations from Langmuir adsorption behaviour and may be an intrinsic property of the substrate surface or a property of the adsorbed reactant (induced heterogeneity). Applications of the treatment are made to reduction of surface oxide species at the noble metals and the significance of hysteresis and time effects in the processes of electrochemical formation and reduction of surface oxide at platinum, rhodium, iridium and palladium is investigated.

Primary Yields and Mechanisms in the Radiolysis of N2O from High Intensity Electron Pulse Irradiations of N2O–O2 Mixtures

1972 ◽  
Vol 50 (10) ◽  
pp. 1557-1567 ◽  
Author(s):  
C. Willis ◽  
A. W. Boyd ◽  
P. E. Bindner
Keyword(s):  
High Intensity ◽  
Reaction Rate ◽  
Electron Pulse ◽  
Rate Data

The yields of N2, O2, NO, and O3 have been measured from the Febetron radiolysis of N2O–O2 mixtures with and without SF6. A mechanism consistent with the yields from 0–100% O2 and with known ionic abundances and reaction rate data has been derived. The major features of this mechanism are both dissociative neutralization of N2O+ and excitation of N2O to give N2(X1Σ) and O(1D) and smaller amounts of N2(B3Π) and O(3P). The large yields of NO and N2 observed are mainly due to reaction of O(1D) with N2O to give both N2 and O2 and NO.

scholarly journals Vinyl ether hydrolysis. XIV. 2-Methoxy-2,3-dihydropyran: concurrent reaction of vinyl ether and acetal functional groups

1980 ◽  
Vol 58 (21) ◽  
pp. 2199-2202 ◽  
Author(s):  
R. A. Burt ◽  
Y. Chiang ◽  
A. J. Kresge
Keyword(s):  
Vinyl Ether ◽  
Isotope Effect ◽  
Reaction Rate ◽  
Functional Group ◽  
Minor Amount ◽  
Cyanoacetic Acid ◽  
Buffer Solutions ◽  
Hydrogen Isotope Effect ◽  
A Minor ◽  
Hydrolysis Of

The hydrolysis of 2-methoxy-2,3-dihydropyran shows a normal isotope effect (kH/kD > 1) under catalysis by the hydrogen ion and gives an accurately linear dependence of reaction rate upon undissociated acid concentration in cyanoacetic acid and formic acid buffer solutions. This substrate, therefore, unlike its higher homolog, 9-methoxyoxacyclonon-2-ene, provides no evidence in support of an anything but a normal mechanism for vinyl ether hydrolysis. Analysis of the hydrogen isotope effect suggests that a minor amount (8%) of this hydrolysis occurs via reaction of the acetal functional group.

scholarly journals Reaction Rate Studies of the Acid Hydrolysis of Some Chromium(III) Complexes. XIII. Water Exchange of mer-Triamminetriaqua- and Amminepentaaquachromium(III). Kinetic cis Effect of Ammonia vs. Water.

1982 ◽  
Vol 36a ◽  
pp. 555-561 ◽  
Author(s):  
L. Mønsted ◽  
O. Mønsted ◽  
Johan Springborg ◽  
Ingeborg Persdotter ◽  
Johan Weidlein ◽  
...  
Keyword(s):  
Acid Hydrolysis ◽  
Reaction Rate ◽  
Water Exchange ◽  
Hydrolysis Of
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