Kinetic of oxidation of methyl orange by vanadium(V) under conditions VO2+ and decavanadates coexist: Catalysis by Triton X-100 micellar medium

2019 ◽  
Author(s):  
Chem Int
Keyword(s):  
Methyl Orange ◽  
Solution Ph ◽  
Vanadium Concentration ◽  
Limiting Behavior ◽  
First Order ◽  
First Order Kinetics ◽  
Ph Range ◽  
Kinetic Pattern ◽  
Triton X ◽  
Kinetics Of

The kinetics of oxidation of methyl orange by vanadium(V) {V(V)} has been investigated in the pH range 2.3-3.79. In this pH range V(V) exists both in the form of decavanadates and VO2+. The kinetic results are distinctly different from the results obtained for the same reaction in highly acidic solution (pH < 1) where V(V) exists only in the form of VO2+. The reaction obeys first order kinetics with respect to methyl orange but the rate has very little dependence on total vanadium concentration. The reaction is accelerated by H+ ion but the dependence of rate on [H+] is less than that corresponding to first order dependence. The equilibrium between decavanadates and VO2+ explains the different kinetic pattern observed in this pH range. The reaction is markedly accelerated by Triton X-100 micelles. The rate-[surfactant] profile shows a limiting behavior indicative of a unimolecular pathway in the micellar pseudophase.

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

scholarly journals Temperature and pH effects on the kinetics of 2-aminophenol auto-oxidation in aqueous solution

2003 ◽  
Vol 1 (3) ◽  
pp. 233-241 ◽  
Author(s):  
Dumitru Oancea ◽  
Mihaela Puiu
Keyword(s):  
Experimental Data ◽  
Activation Energy ◽  
Aqueous Solution ◽  
Ph Effects ◽  
Influence Of Temperature ◽  
First Order ◽  
Incremental Methods ◽  
First Order Kinetics ◽  
Ph Range ◽  
Kinetics Of

AbstractThe kinetics of the auto-oxidation of 2-aminophenol (OAP) to 2-amino-phenoxazin-3-one (APX) was followed in air-saturated aqueous solutions and the influence of temperature and pH on the auto-oxidation rate was studied. The kinetic analysis was based on a spectrophotometric method following the increase of the absorbance of APX. The process follows first order kinetics according to the rate law—d[OAP]/dt=k′[OAP]. The experimental data, within the pH range 4–9.85, were analyzed using both differential and incremental methods. The temperature variation of the overall rate constant was studied at pH=9.85 within the range 25–50°C and the corresponding activation energy was evaluated.

Evaluation of Chlorine for Inactivation of Bioterrorism Agents in Drinking Water

2013 ◽  
Vol 295-298 ◽  
pp. 599-603
Author(s):  
Feng Liu ◽  
Zhong Lin Chen ◽  
Sheng Chang
Keyword(s):  
Drinking Water ◽  
Free Chlorine ◽  
Inactivation Kinetics ◽  
Lag Phase ◽  
Solution Ph ◽  
First Order ◽  
Pseudo First Order ◽  
Ph Range ◽  
Kinetics Of ◽  
Experimental Temperature Range

The object of this paper is to measure the characteristics of the inactivation kinetics of B. subtilis spores-surrogates for B. anthracis spores following the treatment with free chlorine. The results indicated that the inactivation kinetics of B. subtilis spores with free chlorine was characterized by a lag phase followed by a pseudo-first-order rate of inactivation. The magnitude of the lag phase increased and the rate of subsequent inactivation decreased with the decreasing temperature, for the experimental temperature range of 1-30 °C. The same tendency of inactivation kinetics curves was observed for the increasing solution pH, for the experimental pH range of 6-8. The CT concept was proved to be valid for the inactivation kinetics of B. subtilis spores with free chlorine under the conditions investigated. The validity of B. subtilis spores served as conservative surrogates for B. anthracis spore has been finally discussed.

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.

scholarly journals Photoinitiated Polymerization of 2-Hydroxyethyl Methacrylate by Riboflavin/Triethanolamine in Aqueous Solution: A Kinetic Study

2013 ◽  
Vol 2013 ◽  
pp. 1-7 ◽  
Author(s):  
Iqbal Ahmad ◽  
Kefi Iqbal ◽  
Muhammad Ali Sheraz ◽  
Sofia Ahmed ◽  
Tania Mirza ◽  
...  
Keyword(s):  
Initial Rate ◽  
Hydroxyl Group ◽  
Hydroxyethyl Methacrylate ◽  
First Order ◽  
First Order Kinetics ◽  
Rate Of Polymerization ◽  
Rate Of Reaction ◽  
Ph Range ◽  
Kinetics Of ◽  
Increased Activity

The polymerization of 1–3 M 2-hydroxyethyl methacrylate (HEMA) initiated by riboflavin/triethanolamine system has been studied in the pH range 6.0–9.0. An approximate measure of the kinetics of the reaction during the initial stages (~5% HEMA conversion) has been made to avoid the effect of any variations in the volume of the medium. The concentration of HEMA in polymerized solutions has been determined by a UV spectrophotometric method at 208 nm with a precision of ±3%. The initial rate of polymerization of HEMA follows apparent first-order kinetics and the rates increase with pH. This may be due to the presence of a labile proton on the hydroxyl group of HEMA. The second-order rate constants for the interaction of triethanolamine and HEMA lie in the range of 2.36 to  M−1 s−1 at pH 6.0–9.0 suggesting an increased activity with pH. An increase in the viscosity of HEMA solutions from 1 M to 3 M leads to a decrease in the rate of polymerization probably as a result of the decrease in the reactivity of the flavin triplet state. The effect of pH and viscosity of the medium on the rate of reaction has been evaluated.

scholarly journals Comparative Study of Chemical Stability of Two H1Antihistaminic Drugs, Terfenadine and ItsIn VivoMetabolite Fexofenadine, Using LC-UV Methods

2019 ◽  
Vol 2019 ◽  
pp. 1-10
Author(s):  
Anna Gumieniczek ◽  
Anna Berecka-Rycerz ◽  
Rafał Pietraś ◽  
Izabela Kozak ◽  
Karolina Lejwoda ◽  
...  
Keyword(s):  
Comparative Study ◽  
Chemical Stability ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of Degradation ◽  
Effects Of Temperature ◽  
High Doses ◽  
Antihistaminic Drugs ◽  
Kinetics Of

A comparative study of chemical stability of terfenadine (TER) and itsin vivometabolite fexofenadine (FEX) was performed. Both TER and FEX were subjected to high temperature at different pH and UV/VIS light at different pH and then quantitatively analyzed using new validated LC-UV methods. These methods were used to monitor the degradation processes and to determine the kinetics of degradation for both the compounds. As far as the effects of temperature and pH were concerned, FEX occurred more sensitive to degradation than TER. As far as the effects of UV/VIS light and pH were concerned, the both drugs were similarly sensitive to high doses of light. Using all stress conditions, the processes of degradation of TER and FEX followed the first-order kinetics. The results obtained for these two antihistaminic drugs could be helpful in developing their new derivatives with higher activity and stability at the same time.

Oxidation of Nickel(II) and Manganese(II) by Peroxodisulfate in Aqueous Solution in the Presence of Molybdate. Crystal Structure of the (NH4)6[NiMo9O32].6H2O Product

1992 ◽  
Vol 45 (12) ◽  
pp. 1943 ◽  
Author(s):  
SJ Dunne ◽  
RC Burns ◽  
GA Lawrance
Keyword(s):  
Rate Constant ◽  
Linear Dependence ◽  
Ph Dependence ◽  
Order Rate Constant ◽  
X Ray Diffraction ◽  
X Ray ◽  
First Order ◽  
Oxidant Concentration ◽  
Ph Range ◽  
Kinetics Of

Oxidation of Ni2+,aq, by S2O82- to nickel(IV) in the presence of molybdate ion, as in the analogous manganese system, involves the formation of the soluble heteropolymolybdate anion [MMogO32]2- (M = Ni, Mn ). The nickel(IV) product crystallized as (NH4)6 [NiMogO32].6H2O from the reaction mixture in the rhombohedra1 space group R3, a 15.922(1), c 12.406(1) � ; the structure was determined by X-ray diffraction methods, and refined to a residual of 0.025 for 1741 independent 'observed' reflections. The kinetics of the oxidation were examined at 80 C over the pH range 3.0-5.2; a linear dependence on [S2O82-] and a non-linear dependence on l/[H+] were observed. The influence of variation of the Ni/Mo ratio between 1:10 and 1:25 on the observed rate constant was very small at pH 4.5, a result supporting the view that the precursor exists as the known [NiMo6O24H6]4- or a close analogue in solution. The pH dependence of the observed rate constant at a fixed oxidant concentration (0.025 mol dm-3) fits dequately to the expression kobs = kH [H+]/(Ka+[H+]) where kH = 0.0013 dm3 mol-1 s-1 and Ka = 4-0x10-5. The first-order dependence on peroxodisulfate subsequently yields a second-order rate constant of 0.042 dm3 mol-1 s-1. Under analogous conditions, oxidation of manganese(II) occurs eightfold more slowly than oxidation of nickel(II), whereas oxidation of manganese(II) by peroxomonosulfuric acid is 16-fold faster than oxidation by peroxodisulfate under similar conditions.

Kinetics of NO2 air space absorption in isolated rat lungs

1992 ◽  
Vol 73 (5) ◽  
pp. 1939-1945 ◽  
Author(s):  
E. M. Postlethwait ◽  
S. D. Langford ◽  
A. Bidani
Keyword(s):  
Steady State ◽  
Tidal Volume ◽  
Gas Phase ◽  
Initial Rate ◽  
Quasi Steady State ◽  
Closed Chamber ◽  
First Order ◽  
First Order Kinetics ◽  
Rat Lungs ◽  
Kinetics Of

We previously showed, during quasi-steady-state exposures, that the rate of inhaled NO2 uptake displays reaction-mediated characteristics (J. Appl. Physiol. 68: 594–603, 1990). In vitro kinetic studies of pulmonary epithelial lining fluid (ELF) demonstrated that NO2 interfacial transfer into ELF exhibits first-order kinetics with respect to NO2, attains [NO2]-dependent rate saturation, and is aqueous substrate dependent (J. Appl. Physiol. 71: 1502–1510, 1991). We have extended these observations by evaluating the kinetics of NO2 gas phase disappearance in isolated ventilating rat lungs. Transient exposures (2–3/lung at 25 degrees C) employed rebreathing (NO2-air) from a non-compliant continuously stirred closed chamber. We observed that 1) NO2 uptake rate is independent of exposure period, 2) NO2 gas phase disappearance exhibited first-order kinetics [initial rate (r*) saturation occurred when [NO2] > 11 ppm], 3) the mean effective rate constant (k*) for NO2 gas phase disappearance ([NO2] < or = 11 ppm, tidal volume = 2.3 ml, functional residual capacity = 4 ml, ventilation frequency = 50/min) was 83 +/- 5 ml/min, 4) with [NO2] < or = 11 ppm, k* and r* were proportional to tidal volume, and 5) NO2 fractional uptakes were constant across [NO2] (< or = 11 ppm) and tidal volumes but exceeded quasi-steady-state observations. Preliminary data indicate that this divergence may be related to the inspired PCO2. These results suggest that NO2 reactive uptake within rebreathing isolated lungs follows first-order kinetics and displays initial rate saturation, similar to isolated ELF.(ABSTRACT TRUNCATED AT 250 WORDS)

Kinetics and Mechanism of Oxidation of Dimethyl Sulphoxide by Mono- and Di-Substituted N,N-Dichlorobenzenesulphonamides in Aqueous Acetic Acid

2003 ◽  
Vol 58 (8) ◽  
pp. 787-794 ◽  
Author(s):  
B.Thimme Gowda ◽  
K. L. Jayalakshmi ◽  
K. Jyothi
Keyword(s):  
Acetic Acid ◽  
Benzene Ring ◽  
Dimethyl Sulphoxide ◽  
Aqueous Acetic Acid ◽  
Isokinetic Temperature ◽  
Free Energies ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of

In an effort to introduce N,N-dichloroarylsulphonamides of different oxidising strengths, four mono- and five di-substituted N,N-dichlorobenzenesulphonamides are prepared, characterised and employed as oxidants for studying the kinetics of oxidation of dimethyl sulphoxide (DMSO) in 50% aqueous acetic acid. The reactions show first order kinetics in [oxidant], fractional to first order in [DMSO] and nearly zero order in [H+]. Increase in ionic strength of the medium slightly increases the rates, while decrease in dielectric constant of the medium decreases the rates. The results along with those of the oxidation of DMSO by N,N-dichlorobenzenesulphonamide and N,N-dichloro-4- methylbenzenesulphonamide have been analysed. Effective oxidising species of the oxidants employed in the present oxidations is Cl+ in different forms, released from the oxidants. Therefore the introduction of different substituent groups into the benzene ring of the oxidant is expected to affect the ability of the reagent to release Cl+ and hence its capacity to oxidise the substrate. Significant changes in the kinetic and thermodynamic data are observed in the present investigations with change of substituent in the benzene ring. The electron releasing groups such as CH3 inhibit the ease with which Cl+ is released from the oxidant, while electron-withdrawing groups such as Cl enhance this ability. The Hammett equation, log kobs = −3.19 + 1.05 σ , is found to be valid for oxidations by all the p-substituted N,N-dichlorobenzenesulphonamides. The substituent effect on the energy of activation, Ea and log A for the oxidations is also analysed. The enthalpies and free energies of activation correlate with an isokinetic temperature of 320 K.

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