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 ◽  
...  

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.

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.


1966 ◽  
Vol 19 (8) ◽  
pp. 1365 ◽  
Author(s):  
RH Smith ◽  
IR Wilson

Initial rates of reaction for the above oxidation have been measured by a stopped-flow conductance method. Between pH 2 and 3.6, the initial rate of reaction, R, is given by the expression R{[HSO5-]+[SCN-]} = {kb+kc[H+]}[HSO5-]0[SCN-]20+ka[H+]-1[HSO5]20[SCN-]0 As pH increases, there is a transition to a pH-independent rate, first order in each thiocyanate and peroxomonosulphate concentrations.


1992 ◽  
Vol 73 (5) ◽  
pp. 1939-1945 ◽  
Author(s):  
E. M. Postlethwait ◽  
S. D. Langford ◽  
A. Bidani

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)


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.


2020 ◽  
Vol 15 (3) ◽  
pp. 853-860
Author(s):  
K. V. Nagalakshmi ◽  
P. Shyamala

The kinetics of acid hydrolysis of bis(2,2';6',2''–terpyridyl) iron(II) complex has been studied in CTAB/Hexane/Chloroform reverse micelles. The reaction obeys first order kinetics with respect to each of the reactants at all values of W, {W= [H2O]/[CTAB]}. In the reverse micellar medium, the reaction is much slower compared to aqueous medium due to low micropolarity of the water pools which does not facilitate a reaction between reactants of same charge. The effect of variation of W {W=[H2O]/[CTAB]} at constant [CTAB] and variation of [CTAB] at fixed W has been studied. The second order rate constant (k2) of the reaction increases as the value of W increases up to W = 8.88 and remains constant thereafter and it is independent of concentration of [CTAB] at constant W. The variation of rate of reaction with W has been explained by considering variation of micropolarity and ionic strength of water pools of reverse micelles with W. Copyright © 2020 BCREC Group. All rights reserved 


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.


1964 ◽  
Vol 19 (3) ◽  
pp. 522-525 ◽  
Author(s):  
J. A. Morello ◽  
Margot R. Craw ◽  
H. P. Constantine ◽  
R. E. Forster

The rate of removal of oxygen from aqueous solution by sodium dithionite in 0.1 m sodium hydroxide was studied in a rapid-reaction apparatus using a membrane-covered polarographic cell to determine Po2 in the flowing liquid. The measurements were made at 37 C, so that the data would be applicable in studies of the kinetics of oxyhemoglobin in blood. The initial concentrations in the mixed reacting solution were between 8 x 10-5 m and 47.5 x 10-5 m for dithionite, and either 10 x 10-5 m or 47.8 x 10-5 m for O2. The reaction over the first 40 msec was found to be first order with respect to dithionite and zero order with respect to molecular oxygen. The initial rate constant was 42.5 ± sd 3.6 sec-1. oxygen reduction by dithionite; hemoglobin; deoxygenation rate; dithionite-oxygen reaction rate Submitted on June 17, 1963


2012 ◽  
Vol 65 (7) ◽  
pp. 931 ◽  
Author(s):  
Stefan M. Paterson ◽  
David H. Brown ◽  
Jeremy A. Shaw ◽  
Traian V. Chirila ◽  
Murray V. Baker

Activators regenerated by electron-transfer atom-transfer radical polymerization, catalyzed by tris(2-pyridylmethyl)amine/CuBr2 and Na{Cu(Gly3)}, was used to synthesize poly(2-hydroxyethyl methacrylate) sponges from 80 : 20 H2O/2-hydroxyethyl methacrylate mixtures. Polymerization-induced phase separations resulted in sponges having morphologies based on agglomerated polymer droplets. During the synthesis of poly(2-hydroxyethyl methacrylate) sponges, first-order kinetics were observed up to a maximum of ~50 % conversion regardless of the catalyst used. The morphologies of the sponges were dependent on the rate of polymerization, slower polymerization rates resulting in polymers with larger morphological features (pores and polymer droplets).


2017 ◽  
Vol 231 (6) ◽  
Author(s):  
Ranjana Sharma ◽  
Mahender Pal ◽  
K.K. Mishra

AbstractKinetics of the oxidation of N-acetyl-L-cysteine (NAC) by methylene blue (MB) catalyzed by Cu(II) have been investigated in presence of HCl. The reaction follows a first order kinetics in MB while the concentration order in NAC is zero. Hydrogen ions retard the rate of reaction. The reaction involves the participation of nanoparticles as revealed by SEM, XRD and FTIR techniques and a gel-like Cu-NAC network acts like the effective catalyst. The reaction conforms to Eley-Rideal mechanism at lower [NAC] while at higher [NAC], the kinetics are explained by extended Eley-Rideal mechanism. The reaction is regulated by the size and morphology of the nanoparticles and is controlled by the entropy of activation.


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