Micellar catalysed hydrolysis of amides. II. N-Ethyl-4-nitrotrifluoroacetanilide in functional and non-functional micelles

1981 ◽  
Vol 34 (8) ◽  
pp. 1603 ◽  
Author(s):  
CJ O'Conner ◽  
AJ Porter
Keyword(s):  
Surface Tension ◽  
Critical Micelle Concentration ◽  
Rate Constants ◽  
Surfactant Concentration ◽  
Hexadecyltrimethylammonium Bromide ◽  
Dimethyl Ammonium Chloride ◽  
Methylammonium Chloride ◽  
Dimethyl Ammonium ◽  
Hydrolysis Of ◽  
Functional Detergents

The reactivity of N-ethyl-4-nitrotrifluoroacetanilide has been examined in the presence of a non-functional detergent (n- hexadecyltrimethylammonium bromide) and three functional detergents, n-hexadecyl(2-hydroxyethyl)dimethylammoniumchloride, n- hexadecyl(imidazol-4-ylmethyl)dimethyl-ammonium chloride and n-hexadecyl(2-hydroxyethyl)(imidazol-4-ylmethyl)methylammonium chloride, at 293.5 K and in borate buffer (1.3 × 10-3 mol dm-3, pH 9.0). The variation of the rate constants for the overall reaction with surfactant concentration has been analysed in terms of the reactant concentrations and rate constants in each pseudophase, the micelle binding constant and the critical micelle concentration, CMC. Surface tension measurements have been made on solutions of these surfactants. The values of CMC have been measured with, and without, the addition of a kinetic concentration of amide and the results compared with those from the kinetic analysis.

Micellar catalysed hydrolysis of amides. 4-Nitroacetanilide in hexadecyl-trimethylammonium bromide

1980 ◽  
Vol 33 (4) ◽  
pp. 747 ◽  
Author(s):  
CJ O'Conner ◽  
A Tan
Keyword(s):  
Surface Tension ◽  
Critical Micelle Concentration ◽  
Competitive Binding ◽  
Micellar Catalysis ◽  
Hexadecyltrimethylammonium Bromide ◽  
Surface Tension Measurement ◽  
Hexadecyl Trimethylammonium Bromide ◽  
Hydrolysis Of

Surface tension measurement of the critical micelle concentration, CMC, of cationic hexadecyltrimethylammonium bromide, ctab, shows a significant increase on addition of very small amounts of 4- nitroacetanilide. At concentrations above the CMC, ctab catalyses the hydrolysis of 4-nitroacetanilide.The micellar catalysis is inhibited by added salts, especially those of arenesulfonates and bulky carboxylate ions. The kinetics have been analysed in terms of competitive binding of the substrate and the inhibitor to the micelle.

Surface Activity Research of Cationic Gemini Surfactants

2013 ◽  
Vol 690-693 ◽  
pp. 2076-2080
Author(s):  
Zhen Zhong Fan ◽  
Lan Lan Li ◽  
Li Feng Zhang ◽  
Qing Wang Liu
Keyword(s):  
Surface Tension ◽  
Critical Micelle Concentration ◽  
Surface Activity ◽  
Surfactant Concentration ◽  
Gemini Surfactant ◽  
Gemini Surfactants ◽  
Ph Value ◽  
Inorganic Salts ◽  
Cationic Gemini Surfactant ◽  
Cationic Gemini Surfactants

Cationic Gemini surfactant concentration, the inorganic salts added and the pH value of surface tension obtained cationic gemini surfactant critical micelle concentration is 0.4mmol / L;by adding three kinds of inorganic salts NaCl, MgCl2, and Na2SO4 ,which Na2SO4 has the greatest impact on surface tension, followed by MgCl2.The surface minimum tension of the pH ranged from 9 to 11 , indicating that the surface activity of cationic gemini surfactants achieved the highest.

Surface Activity Research of Cationic Gemini Surfactants

2013 ◽  
Vol 652-654 ◽  
pp. 1450-1454
Author(s):  
Zhen Zhong Fan ◽  
Lan Lan Li ◽  
Li Feng Zhang ◽  
Qing Wang Liu
Keyword(s):  
Surface Tension ◽  
Critical Micelle Concentration ◽  
Surface Activity ◽  
Surfactant Concentration ◽  
Gemini Surfactant ◽  
Gemini Surfactants ◽  
Ph Value ◽  
Inorganic Salts ◽  
Cationic Gemini Surfactant ◽  
Cationic Gemini Surfactants

Cationic Gemini surfactant concentration, the inorganic salts added and the pH value of surface tension obtained cationic gemini surfactant critical micelle concentration is 0.4mmol / L;by adding three kinds of inorganic salts NaCl, MgCl2, and Na2SO4 ,which Na2SO4 has the greatest impact on surface tension, followed by MgCl2.The surface minimum tension of the pH ranged from 9 to 11 , indicating that the surface activity of cationic gemini surfactants achieved the highest.

Catalyzed Alkaline Hydrolysis of Substituted Phenyl Acetates

1993 ◽  
Vol 58 (8) ◽  
pp. 1798-1802 ◽  
Author(s):  
Jiří Kulič ◽  
Aleš Ptáček
Keyword(s):  
Alkaline Medium ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Hexadecyltrimethylammonium Bromide ◽  
Hammett Equation ◽  
First Order ◽  
Order Rate ◽  
Iodosobenzoic Acid ◽  
Hydrolysis Of

2-Iodosobenzoic acid forming strong nucleophile in alkaline medium - 1-oxido-1,2-benziodoxol-3(1H)-one, was used as a catalyst of alkaline hydrolysis of substituted phenyl acetates (4-NO2, 3-NO2, 3-Cl, 4-Br, H, 4-CH3, 3-CH3, 4-OCH3, 3-OCH3) in the presence of hexadecyltrimethylammonium bromide as a micellar agent. It was found that the observed first-order rate constants kobs can be correlated by the Hammett equation: log kobs = (-3.29 ± 0.03) + (1.77 ± 0.001) σ.

Kinetics of hydrolysis of peroxodisulphate ions in acidic medium to peroxomonosulphuric acid

1981 ◽  
Vol 46 (5) ◽  
pp. 1229-1236 ◽  
Author(s):  
Jan Balej ◽  
Milada Thumová
Keyword(s):  
Ionic Strength ◽  
Rate Constants ◽  
Acidic Medium ◽  
Measured Data ◽  
Molar Ratios ◽  
Starting Solution ◽  
Kinetics Of Hydrolysis ◽  
Rate Of Hydrolysis ◽  
Kinetics Of ◽  
Hydrolysis Of

The rate of hydrolysis of S2O82- ions in acidic medium to peroxomonosulphuric acid was measured at 20 and 30 °C. The composition of the starting solution corresponded to the anolyte flowing out from an electrolyser for production of this acid or its ammonium salt at various degrees of conversion and starting molar ratios of sulphuric acid to ammonium sulphate. The measured data served to calculate the rate constants at both temperatures on the basis of the earlier proposed mechanism of the hydrolysis, and their dependence on the ionic strength was studied.

Salt effect in hydrolysis of 3-acyl-1,3-diphenyltriazenes

1981 ◽  
Vol 46 (12) ◽  
pp. 3104-3109 ◽  
Author(s):  
Miroslav Ludwig ◽  
Oldřich Pytela ◽  
Miroslav Večeřa
Keyword(s):  
Sodium Chloride ◽  
Temperature Dependence ◽  
Potassium Chloride ◽  
Rate Constants ◽  
Zinc Sulphate ◽  
Salt Effect ◽  
Sodium Sulphate ◽  
Potassium Sulphate ◽  
Lithium Sulphate ◽  
Hydrolysis Of

Rate constants of non-catalyzed hydrolysis of 3-acetyl-1,3-diphenyltriazene (I) and 3-(N-methylcarbamoyl)-1,3-diphenyltriazene (II) have been measured in the presence of salts (ammonium chloride, potassium chloride, lithium chloride, sodium chloride and bromide, ammonium sulphate, potassium sulphate, lithium sulphate, sodium sulphate and zinc sulphate) within broad concentration ranges. Temperature dependence of the hydrolysis of the substrates studied has been measured in the presence of lithium sulphate within temperature range 20° to 55 °C. The results obtained have been interpreted by mechanisms of hydrolysis of the studied substances.

Kinetic study of hydrolysis of benzoates. part xxvii. ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous Bu4NBr

2009 ◽  
Vol 74 (1) ◽  
pp. 29-42 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Signe Vahur ◽  
Oksana Travnikova ◽  
Ilmar A. Koppel
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Pure Water ◽  
Substituent Effects ◽  
Benzoic Acids ◽  
Resonance Effects ◽  
The Media ◽  
Substituted Benzoic Acids ◽  
Hydrolysis Of ◽  
Ortho Substituent

The second-order rate constants k (in dm3 mol–1 s–1) for alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2C6H5, have been measured spectrophotometrically in aqueous 0.5 and 2.25 M Bu4NBr at 25 °C. The substituent effects for para and meta derivatives were described using the Hammett relationship. For the ortho derivatives the Charton equation was used. For ortho-substituted esters two steric scales were involved: the EsB and the Charton steric (υ) constants. When going from pure water to aqueous 0.5 and 2.25 M Bu4NBr, the meta and para polar effects, the ortho inductive and resonance effects in alkaline hydrolysis of phenyl esters of substituted benzoic acids, became stronger nearly to the same extent as found for alkaline hydrolysis of C6H5CO2C6H4-X. The steric term of ortho-substituted esters was almost independent of the media considered. The rate constants of alkaline hydrolysis of ortho-, meta- and para-substituted phenyl benzoates (X-C6H4CO2C6H5, C6H5CO2C6H4-X) and alkyl benzoates, C6H5CO2R, in water, 0.5 and 2.25 M Bu4NBr were correlated with the corresponding IR stretching frequencies of carbonyl group, (ΔνCO)X.

Kinetic Study of Hydrolysis of Benzoates. Part XXVI. Variation of the Substituent Effect with Solvent in Alkaline Hydrolysis of Substituted Alkyl Benzoates

2006 ◽  
Vol 71 (11-12) ◽  
pp. 1557-1570 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Ilmar A. Koppel
Keyword(s):  
Kinetic Study ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Substituent Effect ◽  
Substituent Effects ◽  
Alkyl Substituent ◽  
Solvent Parameters ◽  
Substituent Constants ◽  
Hydrolysis Of ◽  
Main Factor

The second-order rate constants k2 (dm3 mol-1 s-1) for the alkaline hydrolysis of substituted alkyl benzoates C6H5CO2R have been measured spectrophotometrically in aqueous 0.5 M Bu4NBr at 50 and 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH, CH2C6H5, CH2CH2Cl, CH2CH2OCH3, CH2CH3) and in aqueous 5.3 M NaClO4 at 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH). The dependence of the alkyl substituent effects on different solvent parameters was studied using the following equations:      ∆ log k = c0 + c1σI + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆EσI + c7∆YσI + c8∆PσI     ∆ log k = c0 + c1σ* + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆Eσ* + c7∆Yσ* + c8∆Pσ* .  ∆ log k = log kR - log kCH3. σI and σ* are the Taft inductive and polar substituent constants. E, Y and P are the solvent electrophilicity, polarity and polarizability parameters, respectively. In the data treatment ∆E = ES - EH2O , ∆Y = YS - YH2O , ∆P = PS - PH2O were used. The solvent electrophilicity, E, was found to be the main factor responsible for changes in alkyl substituent effects with medium. When σI constants were used, variation of the polar term of alkyl substituents with the solvent electrophilicity E was found to be similar to that observed earlier for meta and para substituents, but twice less when σ* constants were used. The steric term for alkyl substituents was approximately independent of the solvent parameters.

A kinetic standard for precise calibration of spectrophotometer cell temperature.

1981 ◽  
Vol 27 (5) ◽  
pp. 753-755 ◽  
Author(s):  
P A Adams ◽  
M C Berman
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Cell Temperature ◽  
First Order ◽  
Order Rate ◽  
Acid Catalyzed ◽  
Pseudo First Order ◽  
Hydrolysis Of

Abstract We describe a simple, highly reproducible kinetic technique for precisely measuring temperature in spectrophotometric systems having reaction cells that are inaccessible to conventional temperature probes. The method is based on the temperature dependence of pseudo-first-order rate constants for the acid-catalyzed hydrolysis of N-o-tolyl-D-glucosylamine. Temperatures of reaction cuvette contents are measured with a precision of +/- 0.05 degrees C (1 SD).

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