Kinetics and mechanism of covalent addition of S(IV) species to the acridinium cation

1996 ◽  
Vol 74 (3) ◽  
pp. 365-370 ◽  
Author(s):  
Maria P. Ros ◽  
Jesus Thomas ◽  
Guillermo Crovetto ◽  
Juan Llor
Keyword(s):  
Rate Constants ◽  
Carbonyl Compounds ◽  
Nonlinear Least Squares ◽  
Kinetics And Mechanism ◽  
Experimental Conditions ◽  
Ph Profile ◽  
First Order ◽  
Constant Ph ◽  
Ph Range ◽  
Experimental Values

The reaction of acridine with S(IV) species (SO2•H2O, HSO3−, and SO32−) to form the adduct acridine–S(IV) has been studied spectrophotometrically throughout the pH range 2.6–8 in aqueous solutions. The observed pseudo-first-order rate constants, kobs, were determined at 25 °C and ionic strength I = 0.11 M, and the pH profile of the rate reached a maximum at pH ≈ 6.1. At constant pH the kobs values were a linear function of the total S(IV) concentration with slopes that increased significantly with pH. These data are consistent with the rate-determining attack of SO3H− and SO32− upon the C-9 of the acridinium cation. A nonlinear least-squares fitting of the experimental values to the model equation, within the overall pH region studied, yields the pH-independent rate constants k1 = 3.7 ± 0.1 and k2 = (6.24 ± 0.04) × 104 M−1 s−1 for the attack of these two species, respectively. The experimental results agree very well with the kinetic model. Due to the experimental conditions used we did not detect any possible pseudobase formation in the pH range studied. The reactivity of the S(IV) species with acridine follows the order: [Formula: see text] The value obtained for the ratio k1/k2 is similar to the results given for other addition reactions of S(IV) species to the double bond of carbonyl compounds such as benzaldehyde and formaldehyde. Key words: covalent addition, acridine, acridine – S(IV) adducts, kinetics and mechanism.

Kinetics and mechanism of disproportionation and ferricyanide oxidation of the 10-methylacridinium cation in aqueous base

1984 ◽  
Vol 62 (4) ◽  
pp. 729-735 ◽  
Author(s):  
John W. Bunting ◽  
Glenn M. Kauffman
Keyword(s):  
Ionic Strength ◽  
Second Order ◽  
Kinetics And Mechanism ◽  
Oxidation Pathway ◽  
First Order ◽  
Aqueous Base ◽  
Ph Range ◽  
Rate Profile ◽  
Kinetics Of ◽  
Major Oxidation

The kinetics of disproportionation and ferricyanide ion oxidation of the 10-methylacridinium cation have been measured spectrophotometrically over the pH range 9–14 in.20% CH3CN – 80% H2O (v/v) and ionic strength 1.0 at 25 °C. Disproportionation is kinetically second-order in total acridine species. The pH–rate profile is consistent with the rate-determining reaction of one acridinium cation with the pseudobase alkoxide anion derived from a second acridinium cation. Ferricyanide ion oxidation is kinetically first-order in each of ferricyanide ion and total acridine species. The pH–rate profile requires three distinct pathways for the ferricyanide ion oxidation of the 10-methylacridinium cation. For pH < 9.7, rate-determining attack of ferricyanide ion on the neutral pseudobase predominates, while for pH > 12.8 the predominant oxidation pathway involves reaction of ferricyanide ion with the pseudobase alkoxide ion. Between pH 9.7 and 12.8, the major oxidation pathway involves initial disproportionation of the acridinium cation followed by ferricyanide ion oxidation of the 9,10-dihydro-10-methylacridine product. This latter route accounts for a maximum of 69% of the total ferricyanide ion oxidation at pH 11.1.

scholarly journals Removal of Emerging Contaminants in Wastewater by Sonolysis, Photocatalysis and Ozonation

2018 ◽  
Vol 21 (2) ◽  
pp. 98-105 ◽  
Keyword(s):  
Rate Constants ◽  
Photocatalytic Oxidation ◽  
Advanced Oxidation Processes ◽  
Emerging Contaminants ◽  
Removal Rate ◽  
Experimental Conditions ◽  
Oxidation Processes ◽  
First Order ◽  
Performance Variation ◽  
Pseudo First Order

<p>Three different advanced oxidation processes (AOPs) were applied to investigate the removal of emerging contaminants (ECs) i.e. sulfamethoxazole (SMX), diclofenac (DCF) and carbamazepine (CBZ) in synthetically prepared solutions. The degradation of these substances was carried out by ozonation, sonolysis and photocatalytic oxidation, as well as by different combinations of these processes. The objectives of this work were to evaluate the removal efficiency in each AOP and to assess the performance variation of sonolysis in combination with other AOPs. The best performances were achieved by sonocatalysis, which resulted in the removal of the selected pharmaceuticals in the range between 37% and 47%. Under similar experimental conditions, the removal of the selected ECs by single compounds by ozonation was slightly lower than the removal of respective compounds in the mixture. Moreover, pseudo first-order removal rate constants of photocatalytic mineralization were determined as 9.33×10-2, 4.90×10-3, 1.06×10-2 min-1 for SMX, DCF and CBZ, respectively.</p>

Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media

1993 ◽  
Vol 71 (12) ◽  
pp. 2155-2159 ◽  
Author(s):  
Subrata Mukhopadhyay ◽  
Swapan Chaudhuri ◽  
Rina Das ◽  
Rupendranath Banerjee
Keyword(s):  
Free Radicals ◽  
Rate Constant ◽  
Decomposition Rate ◽  
Rate Constants ◽  
Kinetics And Mechanism ◽  
Unimolecular Decomposition ◽  
Decomposition Rate Constant ◽  
Mixed Complexes ◽  
Ph Range ◽  
Oxalate Ion

In the pH range 6.6–8.6, [MnL2(H2O)2]+ and [MnL2(H2O)(OH)] (HL = acetylacetone) oxidize oxalate ion (ox2−) to CO2 through the inner-sphere intermediates [MnL2(ox)]− and [MnL2(OH)(ox′)]2−, where ox′ is a half-bonded (unidentate) oxalate ion. Their rate constants of decomposition are 1.0 × 10−4 s−1 and 11.2 × 10−2 M−1 s−1 at 30 °C and at I = 1.0 M (NaClO4). Decomposition of these mixed complexes produces free radicals, presumably CO2−, which is further oxidized to CO2 by another Mn(III) in a fast step. At pH 4.2, [Mn(ox)3]3− is produced quantitatively when [ox]0 ≥ 0.12 M, which has been characterized spectrally, and its unimolecular decomposition rate constant k (= 2.7 × 10−4s−1 at 30 °C and I = 1.0 M) compares well with that reported earlier (2.44 × 10−4 s−1 at 25 °C and I = 1.0 M).

Kinetics and mechanism of aminolysis of (Z)-4-arylidene-2-phenyl-5(4H)oxazolones

1992 ◽  
Vol 70 (10) ◽  
pp. 2515-2519 ◽  
Author(s):  
Sharifa S. Alkaabi ◽  
Ahmad S. Shawali
Keyword(s):  
Rate Constants ◽  
Activation Parameters ◽  
Order Conditions ◽  
Kinetics And Mechanism ◽  
Hammett Equation ◽  
Third Order ◽  
First Order ◽  
Different Temperatures ◽  
Pseudo First Order ◽  
Kinetics Of

The kinetics of the reactions of a series of (Z)-4-arylidene-2-phenyl-5(4H)oxazolones 1 with n-butylamine and piperidine were studied spectrophotometrically in dioxane, ethanol, and cyclohexane under pseudo-first-order conditions and at different temperatures. The relation k1(obs) = k2[amine] + k3[amine]2 was found applicable for all reactions studied in either dioxane or ethanol. However, in cyclohexane the n-butylaminolysis of 1 followed only third-order kinetics k1(obs) = k3[n-BuNH2]2. The kinetics of the reaction of 1 with n-butylamine in the presence of catalytic amounts of triethylamine in dioxane followed the equation: k1(obs)k2 = [n-BuNH2] + k3[n-BuNH2]2[Formula: see text] [Et3N]. The rate constants k2 and k3 correlated well with the Hammett equation and the corresponding activation parameters were determined. The results were interpreted in terms of a mechanism involving solvent- and amine-catalyzed processes.

THE DECOMPOSITION OF 2-METHYL-Δ2-OXAZOLINE IN AQUEOUS SOLUTION

1963 ◽  
Vol 41 (7) ◽  
pp. 1662-1670 ◽  
Author(s):  
R. Greenhalgh ◽  
R. M. Heggie ◽  
M. A. Weinberger
Keyword(s):  
Aqueous Solution ◽  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Water Concentration ◽  
Acidity Function ◽  
First Order ◽  
Ph Values ◽  
Constant Ph ◽  
Kinetic Expression ◽  
Ph Range

Nuclear magnetic resonance has been used to follow the decomposition of aqueous solutions of 2-methyl-Δ2-oxazoline (0.29 M) at constant pH values in the range −1 to 14. The decomposition is first order with respect to total oxazoline at any specific pH, but deviates from the simple reaction of water with the protonated species above pH 5. At neutral pH values this is shown to be partially due to a second reaction involving 2-methyl-Δ2-oxazoline and O-acetylethanolamine which yields N-2-acetoxyethyl N′-2-hydroxyethyl acetamidate. The decrease in rate constant at pH < 2 is accounted for by variation in the water concentration, which is related to the acidity function. A kinetic expression is derived for the decomposition over the whole pH range studied. The decomposition of the amidate is also discussed.

scholarly journals Photodegradation of levofloxacin in aqueous and organic solvents: A kinetic study

2013 ◽  
Vol 63 (2) ◽  
pp. 223-229 ◽  
Author(s):  
Iqbal Ahmad ◽  
Raheela Bano ◽  
Muhammad Ali Sheraz ◽  
Sofia Ahmed ◽  
Tania Mirza ◽  
...  
Keyword(s):  
Dielectric Constant ◽  
Degradation Rate ◽  
Hplc Method ◽  
Ph Profile ◽  
Degree Of Ionization ◽  
First Order ◽  
First Order Kinetics ◽  
Anionic Species ◽  
Ph Range ◽  
Kinetics Of

The kinetics of photodegradation of levofloxacin in solution on UV irradiation in the pH range 2.0-12.0 has been studied using a HPLC method. Levofloxacin undergoes first-order kinetics in the initial stages of the reaction and the apparent first-order rate constants are of the order of 0.167 to 1.807×10-3 min-1. The rate-pH profile is represented by a curve indicating the presence of cationic, dipolar and anionic species during the reaction. The singly ionized form of the molecule is non-fluorescent and is less susceptible to photodegradation. The increase in the degradation rate in the pH range 5.0-9.0 may be due to greater reactivity of the ionized species existing in that range. The rate appears to vary with a change in the degree of ionization of the species present in a particular pH range and their susceptibility to photodegradation. Above pH 9, the decrease in the rate of photodegradation may be a result of deprotonation of the piperazinyl group. The levofloxacin molecule is more stable in the pH range around 7, which is then suitable for formulation purposes. The photodegradation of levofloxacin was found to be affected by the dielectric constant and viscosity of the medium

Kinetics and mechanism of the oxidation of proline by periodate

1989 ◽  
Vol 67 (4) ◽  
pp. 634-638 ◽  
Author(s):  
Rosa Pascual ◽  
Miguel A. Herraez ◽  
Emilio Calle.
Keyword(s):  
Amino Acid ◽  
Rate Constants ◽  
Reaction Rate ◽  
Ph Dependence ◽  
Kinetics And Mechanism ◽  
Appreciable Amount ◽  
Kinetics Of Oxidation ◽  
Rate Law ◽  
First Order ◽  
Kinetics Of

The kinetics of oxidation of proline by periodate has been studied at pH 1.40–8.83 and 30.0 °C. The reaction rate is first order in both periodate and amino acid, and the overall reaction follows second-order kinetics. There was no evidence for the formation of an appreciable amount of intermediate. The reaction rate is highest at pH 4–7 and the oxidation is catalysed by [Formula: see text] ions. The pH dependence of the reaction rate can be explained in terms of reaction of periodate monoanion and the protonated and dipolar forms of the amino acid. The mechanism proposed and the derived rate law are consistent with the observed kinetics. The rate constants obtained from the derived rate law are in agreement with the observed rate constants, thus justifying the rate law and the proposed mechanistic scheme. Keywords: oxidation of proline, oxidation by periodate.

The kinetics and mechanism of the reaction between nickel(II) and dithiocarbamate ions in dimethyl sulfoxide. Evidence for the ID mechanism for a bidentate uninegative ligand

1978 ◽  
Vol 31 (12) ◽  
pp. 2581 ◽  
Author(s):  
PJ Nichols ◽  
MW Grant
Keyword(s):  
Fourier Transform ◽  
Ionic Strength ◽  
Dimethyl Sulfoxide ◽  
Excellent Agreement ◽  
Rate Constants ◽  
Second Order ◽  
Kinetics And Mechanism ◽  
First Order ◽  
Temperature Dependences ◽  
Mechanism Of The Reaction

13C Fourier-transform N.M.R. has been used to measure the rate of exchange of dimethyl sulfoxide with hexakis(dimethyl sulfoxide)nickel(II) cation. The parameters obtained, kex(25°C)(9.8�4.6) × 103 s-1, ΔH‡ 50�2 kJ mol-1 and ΔS‡ 0�4 J K-1 mol-1, are in excellent agreement with those of the most recent 1H N.M.R. study. The reaction between Ni(Me2SO)62+ and diethyldithiocarbamate (dtc-) gives only Ni(dtc)2. When dtc- is in excess, the rate of formation of Ni(dtc)2 is first order in Ni2+ and dtc-. The ionic-strength and temperature dependences of the second-order rate constants are consistent with the rate-determining formation of an unstable Ni(dtc)+ complex by an ID mechanism.

Effect of pH, Buffer, and Viscosity on the Photolysis of Formylmethylflavin: A Kinetic Study

2013 ◽  
Vol 66 (5) ◽  
pp. 579 ◽  
Author(s):  
Iqbal Ahmad ◽  
Tania Mirza ◽  
Kefi Iqbal ◽  
Sofia Ahmed ◽  
Muhammad Ali Sheraz ◽  
...  
Keyword(s):  
Rate Constants ◽  
Anaerobic Conditions ◽  
First Order ◽  
Phosphate Ions ◽  
First Order Kinetics ◽  
Ph Buffer ◽  
Ph Range ◽  
Kinetics Of ◽  
Aerobic And Anaerobic ◽  
Aerobic And Anaerobic Conditions

The kinetics of the photolysis of formylmethylflavin, a major intermediate product in the aerobic and anaerobic photolysis of riboflavin, was studied in the pH range 2.0–11.0. Formylmethylflavin and its photoproducts, lumichrome and lumiflavin, were determined in degraded solutions using a specific multicomponent spectrophotometric method. The photolysis of formylmethylflavin in alkaline medium takes place by first-order kinetics and the rate constants (kobs) at pH 7.5–11.0 range from 0.27 × 10–4 to 3.88 × 10–4 and 0.36 × 10–4 to 5.63 × 10–4 s–1 under aerobic and anaerobic conditions respectively. In acid medium, the photolysis involves a second-order mechanism and the rate constants at pH 2.0–7.0 range from 1.37 to 2.11 and 2.03 to 2.94 M–1 s–1 under aerobic and anaerobic conditions respectively. The rate–pH profiles for the photolysis reactions indicate the highest rate of formylmethylflavin degradation is at ~pH 4 and above pH 10. In the alkaline region, the increase in rate with pH is due to higher reactivity of the flavin triplet state. The photolysis of formylmethylflavin is catalyzed by phosphate ions and is affected by the solvent viscosity.

Kinetics and mechanism of the decarboxylation of pyrimidine-2-carboxylic acid in aqueous solution

1977 ◽  
Vol 55 (13) ◽  
pp. 2478-2481 ◽  
Author(s):  
Gerald E. Dunn ◽  
Edward A. Lawler ◽  
A. Brian Yamashita
Keyword(s):  
Carbon Dioxide ◽  
Aqueous Solution ◽  
Carboxylic Acid ◽  
Rate Constants ◽  
Kinetics And Mechanism ◽  
First Order ◽  
Order Rate ◽  
Pseudo First Order ◽  
Positively Charged

Pseudo-first-order rate constants for the decarboxylation of pyrimidine-2-carboxylic acid have been determined at 65 °C in aqueous solution over the acidity range pH = 2 to H0 = −9.5. Rate constants increase rapidly from pH = 2 to H0 = −3, then remain constant. This behaviour can be accounted for by a Hammick-type mechanism in which monoprotonated pyrimidine-2-carboxylic acid loses carbon dioxide to form an ylide (stabilized by the adjacent positively charged nitrogens) which rapidly converts to pyrimidine.

Sign in / Sign up

Export Citation Format

Share Document