Kinetic studies of Dakin oxidation of o- and p-hydroxyacetophenones

1977 ◽  
Vol 55 (1) ◽  
pp. 102-110 ◽  
Author(s):  
M. B. Hocking ◽  
J. H. Ong

Rates of oxidation of aqueous o-, and p-hydroxyacetophenone with alkaline hydrogen peroxide to yield catechol and hydroquinone, respectively, have been followed spectrophotometri-cally. Both ketones showed smooth pseudo first-order behaviour, the ortho isomer yielding rate constants in the range 2.6 to 6.6 × 10−2 min−1 at 0 °C, and the para isomer of 0.73 to 7.10 × 10−2 min−1 at 35 °C for the concentrations of hydrogen peroxide and base used. The order in hydrogen peroxide was, unexpectedly, found to be 1.4. A simple test established that this fractional order was probably not the result of hydrogen peroxide involvement in simultaneous first- and second-order processes of differing rates. Other plausible pathways to explain this are proposed.

2011 ◽  
Vol 383-390 ◽  
pp. 2945-2950 ◽  
Author(s):  
Jie Zhang ◽  
Shi Long He ◽  
Mei Feng Hou ◽  
Li Ping Wang ◽  
Li Jiang Tian

The kinetics of TBBPA degradation by ozonation in semi-batch reactor was studied. The reaction rate constants of TBBPA with O3 and •OH were measured by means of direct ozone attack and competition kinetics, and the values of which were 6.10 l/(mol•s), 4.8×109 l/(mol•s), respectively. Results of kinetic studies showed that TBBPA degradation by ozonation under the different conditions tested followed the pseudo-first-order. The values of apparent rate constant of TBBPA degradation increased with the increase of ozone dosage and pH, but decreased with the increase of initial TBBPA concentration.


1974 ◽  
Vol 143 (3) ◽  
pp. 587-590 ◽  
Author(s):  
Barry J. Kitchen ◽  
Patrick Andrews

The inhibition of lactose synthetase A protein by p-hydroxymercuribenzoate at pH7.5 and 25°C, which involves the reaction of one molecule of inhibitor with each molecule of enzyme, was decreased in rate by UDP-galactose, especially in the presence of Mn2+. Pseudo-first-order rate constants for the reaction between 0.1mm-p-hydroxymercuribenzoate and free enzyme, the enzyme–UDP-galactose complex and the enzyme–Mn2+–UDP-galactose complex were 4.4×10−2, 1.9×10−2 and 0.3×10−2min−1 respectively. The results also indicated that dissociation constants for UDP-galactose in the enzyme–UDP-galactose and enzyme–Mn2+–UDP-galactose complexes were 313 and 16μm respectively, the latter value being similar to the Km for UDP-galactose in the lactose synthetase reaction. The protective effect of UDP-galactose and the role of Mn2+ ions in lactose synthetase are discussed.


Synthesis ◽  
2022 ◽  
Author(s):  
Herbert Mayr ◽  
Manfred Hartnagel ◽  
Armin R. Ofial

AbstractDiazocyclopentadiene reacts with benzhydrylium ions (Ar2CH+) to give 2,5-dibenzhydryl-substituted diazocyclopentadienes. The kinetics have been determined photometrically in dichloromethane under pseudo-first-order conditions using diazocyclopentadiene in excess. Plots of the second-order rate constants (log k 2) versus the electrophilicity parameters E of the benzhydrylium ions gave the nucleo­philicity parameter N = 4.84 and susceptibility s N = 1.06 for diazo­cyclopentadiene according to the correlation log k(20 °C) = s N(E + N). Diazocyclopentadiene thus has a similar nucleophilic reactivity as pyrrole. Previously reported electrophilic substitutions of diazocyclopentadiene are rationalized by these parameters and new reaction possibilities are predicted.


2014 ◽  
Vol 625 ◽  
pp. 901-906
Author(s):  
Anisa Ur Rahmah ◽  
Sabtanti Harimurti ◽  
Abdul Aziz Omar ◽  
Thanabalan Murugesan

–Oxytetracycline (OTC), a widely used of veterinary antibiotic, was degraded inside a UV/H2O2system. Kinetic study was conducted at 30°C of temperature and pH 6.37, as suggested by the previous optimization experiment. About 250, 375 and 500 ppm initial OTC concentration were used for the kinetic studies, at H2O2concentration of 0.116 M. The experimental data were plotted against the pseudo zero-th, first and second order of kinetic. Based on regression coefficient value, the data was well fitted with the pseudo first order of kinetic. The calculated value ofkobswas 0.181 min-1.


1981 ◽  
Vol 27 (5) ◽  
pp. 753-755 ◽  
Author(s):  
P A Adams ◽  
M C Berman

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).


1987 ◽  
Author(s):  
Moideen P Jamaluddin

Platelet aggregation kinetics, according to the particle collision theory, generally assumed to apply, ought to conform to a second order type of rate law. But published data on the time-course of ADP-induced single platelet recruitment into aggregates were found not to do so and to lead to abnormal second order rate constants much larger than even their theoretical upper bounds. The data were, instead, found to fit a first order type of rate law rather well with rate constants in the range of 0.04 - 0.27 s-1. These results were confirmed in our laboratory employing gelfiltered calf platelets. Thus a mechanism much more complex than hithertofore recognized, is operative. The following kinetic scheme was formulated on the basis of information gleaned from the literature.where P is the nonaggregable, discoid platelet, A the agonist, P* an aggregable platelet form with membranous protrusions, and P** another aggregable platelet form with pseudopods. Taking into account the relative magnitudes of the k*s and assuming aggregation to be driven by hydrophobic interaction between complementary surfaces of P* and P** species, a rate equation was derived for aggregation. The kinetic scheme and the rate equation could account for the apparent first order rate law and other empirical observations in the literature.


2009 ◽  
Vol 59 (7) ◽  
pp. 1361-1369 ◽  
Author(s):  
Edison Gil Pavas ◽  
Miguel Ángel Gómez-García

This work deals with the treatment of the wastewaters resulting from the process of dyeing flowers. In some local cases for growing flowers near to Medellín (Colombia), wastewater color was found to be one of the main problems in meeting local effluent standards. Wastewaters were treated by photodegradation process (which includes photocatalysis) to achieve the degradation of dyes mixture and organic matter in the wastewater. A multifactorial experimental design was proposed, including as experimental factors the following variables: pH, and the concentration of both catalyst (TiO2) and hydrogen peroxide (H2O2). According to the obtained results, at the optimized variables values, it is possible to reach a 99% reduction of dyes, a 76.9% of mineralization (TOC) and a final biodegradability of 0.834. Kinetic analysis allows proposing a pseudo first order reaction for the reduction, the mineralization, and the biodegradation processes.


Sign in / Sign up

Export Citation Format

Share Document