Evidence for general base catalysis by protic solvents in a kinetic study of alcoholyses and hydrolyses of 1-(phenoxycarbonyl)pyridinium ions under both solvolytic and non-solvolytic conditions

2009 ◽  
Vol 74 (1) ◽  
pp. 43-55 ◽  
Author(s):  
Dennis N. Kevill ◽  
Byoung-Chun Park ◽  
Jin Burm Kyong
Keyword(s):  
Second Order ◽  
Base Catalysis ◽  
Substitution Reactions ◽  
Third Order ◽  
Methoxy Derivative ◽  
First Order ◽  
General Base ◽  
Protic Solvents ◽  
Kinetics Of ◽  
Pyridinium Ions

The kinetics of nucleophilic substitution reactions of 1-(phenoxycarbonyl)pyridinium ions, prepared with the essentially non-nucleophilic/non-basic fluoroborate as the counterion, have been studied using up to 1.60 M methanol in acetonitrile as solvent and under solvolytic conditions in 2,2,2-trifluoroethan-1-ol (TFE) and its mixtures with water. Under the non- solvolytic conditions, the parent and three pyridine-ring-substituted derivatives were studied. Both second-order (first-order in methanol) and third-order (second-order in methanol) kinetic contributions were observed. In the solvolysis studies, since solvent ionizing power values were almost constant over the range of aqueous TFE studied, a Grunwald–Winstein equation treatment of the specific rates of solvolysis for the parent and the 4-methoxy derivative could be carried out in terms of variations in solvent nucleophilicity, and an appreciable sensitivity to changes in solvent nucleophilicity was found.

Kinetics of cyclization of S-ethoxycarbonylmethylisothiouronium chloride to 2-imino-4-thiazolidone

1979 ◽  
Vol 44 (3) ◽  
pp. 912-917 ◽  
Author(s):  
Vladimír Macháček ◽  
Said A. El-bahai ◽  
Vojeslav Štěrba
Keyword(s):  
Hydrochloric Acid ◽  
Dilute Hydrochloric Acid ◽  
Base Catalysis ◽  
General Base ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Kinetics Of Formation ◽  
Acid Catalyzed ◽  
Rate Limiting ◽  
Kinetics Of

Kinetics of formation of 2-imino-4-thiazolidone from S-ethoxycarbonylmethylisothiouronium chloride has been studied in aqueous buffers and dilute hydrochloric acid. The reaction is subject to general base catalysis, the β value being 0.65. Its rate limiting step consists in acid-catalyzed splitting off of ethoxide ion from dipolar tetrahedral intermediate. At pH < 2 formation of this intermediate becomes rate-limiting; rate constant of its formation is 2 . 104 s-1.

Panicle, spikelet, and floret development in orchardgrass (Dactylis glomerata)

1993 ◽  
Vol 71 (4) ◽  
pp. 523-532 ◽  
Author(s):  
Joanna Fraser ◽  
Eric G. Kokko
Keyword(s):  
Electron Microscopy ◽  
Scanning Electron Microscopy ◽  
Unique Feature ◽  
Dactylis Glomerata ◽  
Bilateral Symmetry ◽  
Second Order ◽  
Third Order ◽  
First Order ◽  
Lateral Branches ◽  
Scanning Electron

The initial stages of panicle, spikelet, and floret development in field-grown 'Kay' orchardgrass were examined using scanning electron microscopy. Spikelets arose from a complex multilevelled sequence of initiation from branch apices. Spikelets developed indirectly in a two-tiered progression: (i) an acropetal and basipetal sequence of first order, second-order, and third-order inflorescence apices, and (ii) an acropetal development within subclusters of higher-order lateral branch inflorescence apices. The panicle had the unique feature of dorsiventrality as well as bilateral symmetry. The basal apex from first-order, second-order, or third-order apices developed on the same side of the main axis as the first-order apex. The two glumes subtending each spikelet primordium developed alternately and acropetally. Development and initiation of florets within spikelets was basipetal within the panicle, basipetal within clusters and subclusters of spikelets on lateral branches, and acropetal within spikelets. Within florets, paleas developed later than lemmas. Key words: Dactylis glomerata, cocksfoot, scanning electron microscopy, development, panicle.

scholarly journals Kinetics of Phenolic Compounds Modification during Maize Flour Fermentation

Molecules ◽  
2021 ◽  
Vol 26 (21) ◽  
pp. 6702
Author(s):  
Oluwafemi Ayodeji Adebo ◽  
Ajibola Bamikole Oyedeji ◽  
Janet Adeyinka Adebiyi ◽  
Chiemela Enyinnaya Chinma ◽  
Samson Adeoye Oyeyinka ◽  
...  
Keyword(s):  
Phenolic Compounds ◽  
Phenolic Acids ◽  
Kinetic Models ◽  
Titratable Acidity ◽  
Second Order ◽  
Soluble Solids ◽  
Maize Flour ◽  
First Order ◽  
Compound Modification ◽  
Kinetics Of

This study aimed to investigate the kinetics of phenolic compound modification during the fermentation of maize flour at different times. Maize was spontaneously fermented into sourdough at varying times (24, 48, 72, 96, and 120 h) and, at each point, the pH, titratable acidity (TTA), total soluble solids (TSS), phenolic compounds (flavonoids such as apigenin, kaempferol, luteolin, quercetin, and taxifolin) and phenolic acids (caffeic, gallic, ferulic, p-coumaric, sinapic, and vanillic acids) were investigated. Three kinetic models (zero-, first-, and second-order equations) were used to determine the kinetics of phenolic modification during the fermentation. Results obtained showed that fermentation significantly reduced pH, with a corresponding increase in TTA and TSS. All the investigated flavonoids were significantly reduced after fermentation, while phenolic acids gradually increased during fermentation. Among the kinetic models adopted, first-order (R2 = 0.45–0.96) and zero-order (R2 = 0.20–0.82) equations best described the time-dependent modifications of free and bound flavonoids, respectively. On the other hand, first-order (R2 = 0.46–0.69) and second-order (R2 = 0.005–0.28) equations were best suited to explain the degradation of bound and free phenolic acids, respectively. This study shows that the modification of phenolic compounds during fermentation is compound-specific and that their rates of change may be largely dependent on their forms of existence in the fermented products.

scholarly journals The alcoholysis of 1,2,2-trimethylpropyl-methylfluorophosphonate

2000 ◽  
Vol 65 (12) ◽  
pp. 857-866
Author(s):  
Mladjen Micevic ◽  
Slobodan Petrovic
Keyword(s):  
Kinetic Data ◽  
Reaction Rate ◽  
Frequency Factor ◽  
Reaction Rate Constant ◽  
Order Reaction ◽  
Activation Entropy ◽  
Second Order Reaction ◽  
Third Order ◽  
First Order ◽  
Kinetics Of

The alcoholysis of 1,2,2-trimethylpropyl-methylfluorophosphonate (soman) was examined with a series of alkoxides and in corresponding alcohols: methanol, ethanol, 1-propanol, 2-propanol, 2-methoxyethanol and 2-ethoxyethanol. Soman reacts with the used alkoxides in a second order reaction, first order in each reactant. The kinetics of the reaction between 1,2,2-trimethylpropyl-methylfluorophosphonate and ethanol in the presence of diethylenetriamine was also examined. A third order reaction rate constant was calculated, first order in each reactant. The activation energy, frequency factor and activation entropy were determined on the basis of the kinetic data.

A Note on Homogeneous Dendrites

1968 ◽  
Vol 11 (1) ◽  
pp. 85-93 ◽  
Author(s):  
Z. A. Melzak
Keyword(s):  
Branch Point ◽  
Rooted Tree ◽  
Second Order ◽  
Third Order ◽  
First Order ◽  
Graph Theoretic ◽  
Order Branch

In graph - theoretic terms a homogeneous p-dendrite, p ≥ 2, is defined as a finite singly-rooted tree in which the root has valency 1 while every other vertex has valency 1 or p. More descriptively, a homogeneous p-dendrite may be imagined to start from its root as the main, or 0th order, branch which proceeds to the first - order branch point where it gives rise top first - order branches. Each of these either terminates at its other end (which is a second-order branch point) or it splits there again into p branches (which are of third order), and so on. The order of the dendrite is the highest order of a branch present in it. For completeness, a 0-th order dendrite is also allowed, this consists of the 0-th order branch alone.

scholarly journals Adsorption purification of waste water from chromium by ferrite manganese

2020 ◽  
Vol 168 ◽  
pp. 00026
Author(s):  
Liliia Frolova ◽  
Mykola Kharytonov ◽  
Iryna Klimkina ◽  
Oleksandr Kovrov ◽  
Andrii Koveria
Keyword(s):  
Adsorption Process ◽  
Uv Spectroscopy ◽  
Second Order ◽  
Waste Waters ◽  
Equilibrium Isotherms ◽  
X Ray ◽  
First Order ◽  
Freundlich Isotherms ◽  
Pseudo Second Order ◽  
Kinetics Of

Plasma method is used to synthesize manganese ferrite. The basic properties of ferrite are determined by IR spectroscopy, UV spectroscopy, X-ray phase analysis, vibration magnetometry. The paper shows that the use of magnetically controlled sorbent allows to purify waste waters from chromium (III). The process of adsorption of chromium cations (III) is investigated. The kinetics of the process is studied. To describe the equilibrium isotherms, the experimental data are analysed by the models of Langmuir, Freundlich isotherms. Pseudo-first order, pseudo-second-order, and Weber-Morris are used to elucidate the kinetic parameters and mechanism of the adsorption process. It has been established that the removal of Cr (III) cations is described by the pseudo-second order of the Langmuir reaction and mechanism.

Kinetics and Activation Parameters for the Alkaline Aqueous Rearrangement of Trichorfon [O,O-Dimethyl-(2,2,2-Trichloro-1-Hydroxyethyl) Phosphonate] to Dichlorvos [O,O-Dimethyl-O-(2,2-Dichloroethenyl)Phosphate]

2001 ◽  
Vol 36 (3) ◽  
pp. 589-604 ◽  
Author(s):  
Julian M. Dust ◽  
Christopher S. Warren
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Activation Parameters ◽  
Base Catalysis ◽  
Rearrangement Product ◽  
Exponential Factor ◽  
First Order ◽  
Pseudo First Order ◽  
Order Plot ◽  
Kinetics Of

Abstract The kinetics of the alkaline rearrangement of O,O-dimethyl-(2,2,2-trichloro-1- hydroxyethyl)phosphonate, (trichlorfon, 1), the active insecticidal component in such formulations as Dylox, was followed at 25±0.5°C by high pressure liquid chromatography (UV-vis detector, 210 nm). The rearrangement product, O,Odimethyl- O-(2,2-dichloroethenyl)phosphate (dichlorovos, 2), which is a more potent biocide than trichlorfon, undergoes further reaction, and the kinetics, consequently, cannot be treated by a standard pseudo-first-order plot. A two-point van't Hoff (initial rates) method was used to obtain pseudo-first-order rate constants (kѱ) at 25, 35 and 45°C: 2.6 × 10-6, 7.4 × 10-6 and 2.5 × 10-5 s-1, respectively. Arrhenius treatment of this data gave an activation energy (Ea) of 88 kJ·mol-1 with a pre-exponential factor (A) of 5.5 × 109 s-1. Kinetic trials at pH 8.0 using phosphate and tris buffer systems show no buffer catalysis in this reaction and indicate that the rearrangement is subject to specific base catalysis. Estimates are reported for pseudo-first-order half-lives for trichlorfon at pH 8.0 for environmental conditions in aqueous systems in the Corner Brook region of western Newfoundland, part of the site of a recent trichlorfon aerial spray program.

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