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 ◽  
...  

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.

2019 ◽  
Author(s):  
Chem Int

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.


2018 ◽  
Author(s):  
Andrew C. Mitchell ◽  
Erika J. Espinosa-Ortiz ◽  
Stacy L. Parks ◽  
Adrienne Phillips ◽  
Alfred B. Cunningham ◽  
...  

2008 ◽  
Vol 57 (6) ◽  
pp. 901-907 ◽  
Author(s):  
H. Yasui ◽  
K. Komatsu ◽  
R. Goel ◽  
Y. Y. Li ◽  
T. Noike

For plant wide modelling of wastewater treatment, it is necessary to develop a suitable state variables interface for integrating state of the art models of ASM and ADM1. ADM1 currently describes such an interface, however, its suitability needs to be experimentally evaluated. In this study, we characterised activated sludge under aerobic and anaerobic conditions to obtain representative state variables for both models. ASM state variables of XS, XH and XI (as obtained from aerobic tests) and ADM1 state variables of XC and XI (as obtained from anaerobic tests) were then correlated to assess the suitability of current interface. Based on the seven datasets of this study and seven datasets from literatures, it was found that in general ASM state variables were well correlated to the state variables of ADM1. The ADM1 state variable of XC could be correlated to the sum of state variables of XS and XH, while XI in both the models showed direct correspondence. It was also observed that the degradation kinetics of XC under anaerobic condition could be better described by individual degradation kinetics of XS and XH. Therefore, to establish a one to one correspondence between ASM and ADM1 state variables and better description of degradation kinetics in ADM1, replacing the composite variable of XC by the state variables of XS and XH is recommended.


2008 ◽  
Vol 55-57 ◽  
pp. 757-760 ◽  
Author(s):  
A. Kleawkla ◽  
Robert Molloy ◽  
W. Naksata ◽  
Winita Punyodom

Two novel tin(II) alkoxides, namely: tin(II) hexoxide, Sn(OC6H13)2, and tin(II) octoxide, Sn(OC8H17)2, have been synthesized for use as coordination-insertion initiators in the bulk ring-opening polymerization of ε-caprolactone. The kinetics of the polymerization reactions were studied at 140 °C by dilatometry. It was found that both alkoxides were slow to dissolve in the ε-caprolactone monomer due to their molecular aggregation in the solid state. As a result, the slow solubilization of the initiators gave rise to deviations from the expected first-order kinetics. Instead, the kinetic results adhered more closely to zero-order kinetics with apparent zero-order rate constants k0 of 6.58 x 10-2 and 4.63 x 10-2 mol l-1 min-1 for the hexoxide and octoxide respectively


2013 ◽  
Vol 63 (2) ◽  
pp. 223-229 ◽  
Author(s):  
Iqbal Ahmad ◽  
Raheela Bano ◽  
Muhammad Ali Sheraz ◽  
Sofia Ahmed ◽  
Tania Mirza ◽  
...  

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


2003 ◽  
Vol 1 (3) ◽  
pp. 233-241 ◽  
Author(s):  
Dumitru Oancea ◽  
Mihaela Puiu

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.


2007 ◽  
Vol 95 (10) ◽  
Author(s):  
N. L. Banik ◽  
R. A. Buda ◽  
S. Bürger ◽  
Jens Volker Kratz ◽  
N. Trautmann

The sorption of tetravalent plutonium onto kaolinite, a clay mineral, has been studied as a function of pH. The sorption studies have been performed by batch experiments under aerobic and anaerobic conditions (glove box). A pH range of 0–11 has been investigated with plutonium concentrations of 3.5 × 10


1977 ◽  
Vol 23 (9) ◽  
pp. 1527-1530 ◽  
Author(s):  
R M Shoucri ◽  
M Pouliot

Abstract The Jaffé reaction for creatinine assay appears to follow pseudo-first-order kinetics; first-order rate constants are different for different samples. Rate constants for 10 different serum samples varied from a low value of 0.0040 +/- 0.0003 s-1 to 0.0084 +/- 0.0008 s-1. We describe an approach for determining first-order rate constants from kinetic data and discuss the effects of the above observations on the mathematical formulations required for reliable kinetic determinations of creatinine.


1984 ◽  
Vol 62 (8) ◽  
pp. 971-975 ◽  
Author(s):  
J. H. Carey ◽  
M. E. Fox ◽  
B. G. Brownlee ◽  
J. L. Metcalfe ◽  
R. F. Platford

The disappearance rates of 2,4- and 3,4-dichlorophenol in a small stream were studied and were shown to be first order with respect to either distance or time of flow. Both chlorophenols disappeared at approximately the same rate with average half-lives in the stream of about 4 h. The absence of seasonal variability in the rate constants along with the observance of first order kinetics over several ecological zones of the stream led to the conclusion that the rate controlling factor was not biological. It is suggested that the disappearance was due to degradation within the biofilm covering the stream bed and that the rate is controlled by diffusion of the chlorophenols across the water–biofilm interface.


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