Methylparaben chlorination in the presence of bromide ions and ammonia: kinetic study and modeling.

The impacts of chlorination on methylparaben (MP) removal, as well as of bromide and ammonia on the MP elimination kinetics, were studied. Bromide and ammonia react with chlorine and are promptly transformed into bromine and chloramines, respectively. Rate constants of chlorine, bromine, and monochloramine with MP were determined under different pH conditions. At pH 8.5, the apparent second-order rate constants of MP reactions with chlorine and bromine were found to be 3.37(±0.50) × 101 and 2.37 (±0.11) × 106 M-1.s-1 for kChlorine/MP and kBromine/MP, respectively, yet there was low reactivity with monochloramine ([Formula: see text] = 0.045 M-1.s-1). Regarding chlorination and bromination, in order to gain further insight into the observed pH-dependence of the reaction, the elementary reactions were considered and the corresponding second-order rate constants were calculated. The experimental and modeled values were quite consistent under these conditions. Then, chlorination experiments with different bromide and/or ammonia concentrations were performed to assess the impact of inorganic water content on MP elimination and a kinetic model was designed to assess MP degradation. Under these conditions, MP degradation was found to be enhanced in the presence of bromide whereas it was inhibited in the presence of ammonia, and the overall impact was pH dependent.

Oxidation of 2-aminophenol to 2-amino-3H-phenoxazin-3-one with monochloramine in aqueous environment: A new method for APO synthesis?

Reaction of 2-aminophenol (2AP) with monochloramine in aqueous solution was investigated at pH 8.5 and 25 °C, with an excess of monochloramine. 2-Amino-3H-phenoxazin-3-one (APO) was the major product formed in about 70% yield. Despite low formation yields, adsorbable organic halides (AOX) were also formed over reaction time.

Kinetics of Chlorination of Benzophenone-3 in the Presence of Bromide and Ammonia.

The aim of this study was to assess the impact of chlorination on the degradation of one of the most commonly used UV filters (benzophenone-3 (BP-3)) and the effects of bromide and ammonia on the kinetics of BP-3 elimination. Bromide and ammonia are rapidly converted to bromine and chloramines during chlorination. At first, the rate constants of chlorine, bromine and monochloramine with BP-3 were determined at various pH levels. BP-3 was found to react rapidly with chlorine and bromine, with values of apparent second order rate constants equal to 1.25(±0.14) × 10(3) M(-1)·s(-1) and 4.04(±0.54) × 10(6) M(-1)·s(-1) at pH 8.5 for kChlorine/BP-3 and kBromine/BP-3, respectively, whereas low monochloramine reactivity was observed (kNH2Cl/BP-3 = 0.112 M(-1)·s(-1)). To assess the impact of the inorganic content of water on BP-3 degradation, chlorination experiments with different added concentrations of bromide and/or ammonia were conducted. Under these conditions, BP-3 degradation was found to be enhanced in the presence of bromide due to the formation of bromine, whereas it was inhibited in the presence of ammonia. However, the results obtained were pH dependent. Finally, a kinetic model considering 18 reactions was developed using Copasi to estimate BP-3 degradation during chlorination in the presence of bromide and ammonia.

Concentration levels of urea in swimming pool water and reactivity of chlorine with urea.

This study investigated the reactivity of chlorine with urea which is the main nitrogen contaminant introduced into swimming pool water by bathers. In the first part of this study, analyses showed that the mean concentrations of urea and TOC determined from 50 samples of municipal swimming pool were equal to 18.0 µM (s.d. 11.7) and 3.5 mg C L(-1) (s.d. 1.6), respectively. The mean value for the urea contribution to the TOC content was 6.3% (s.d. 3.3). The rate of decomposition of urea in swimming pool water measured during the closure time of the facility was very slow (decay at the rate of ≈ 1% per hour in the presence of 1.6-1.8 mg L(-1) of free chlorine). In the second part of this work, experiments carried out with phosphate buffered solutions of urea ([Urea](0) = 1 mM; [Cl(2)](0)/[Urea](0): 0.5-15 mol/mol; pH 7.4 ± 0.2; reaction time: 0-200 h) showed that long term chlorine demand of urea was about 5 mol Cl(2)/mol of urea. Chlorination led to a complete mineralization of organic carbon into CO(2) for a chlorine dose of 3.5 mol/mol and to the formation of 0.7-0.8 mol NO(3)(-)/mol of urea for chlorine dose of 8-10 mol/mol. Experiments conducted with dilute solutions of urea ([Urea](0) = 50 µM; pH ≈ 7.3) confirmed that the degradation rate of urea by chlorine is very slow under conditions simulating real swimming pool water.

Effect of some parameters on the formation of chloroform during chloramination of aqueous solutions of resorcinol.

The effects of various factors (N/Cl ratio used to prepare monochloramine, monochloramine doses, pH and contact time) on the monochloramine demand and on the chloroform yield during chloramination of resorcinol have been investigated. Chloramination experiments were carried out at 24+/-1 degrees C, at pH values ranging from 6.5 to 12 using a bicarbonate/carbonate buffer and preformed monochloramine solutions prepared at pH 8.5 with N/Cl ratios ([NH(4)Cl](0)/[Total free Cl(2)](0) ranging from 1.0 to 150 mol/mol). Kinetic experiments ([Resorcinol](0)=5 or 100 microM, [NH(2)Cl](0)/[Resorcinol](0)=20 mol/mol, pH=8.5+/-0.1) showed a slow increase of the monochloramine consumption with reaction time. The monochloramine demands after reaction times of 7 days ([Resorcinol](0)=100 microM) and 14 days ([Resorcinol](0)=5 microM) were equal to 8.5 mol of NH(2)Cl/mole of resorcinol and were higher than the chlorine demands (approximately 7.3 mol/mol). Chloroform yields from monochloramination of resorcinol were lower than 8% (<80 mmol of CHCl(3)/mole of resorcinol) and were less than the yields obtained by chlorination (0.9-0.95 mol/mol). Chloroform productions increased with increasing monochloramine dose and reaction time and decreased with increasing pH values within the pH range 6.5-10. Chloroform formation markedly decreased when the N/Cl ratio increased from 1 to 1.5 mol/mol and was suppressed at N/Cl>100 mol/mol. The data obtained in the present work suggest that free chlorine released from monochloramine hydrolysis plays a significant role on the formation of chloroform during chloramination of resorcinol at N/Cl ratios close to unity (1.0

Effect of dissolved oxygen on the photodecomposition of monochloramine and dichloramine in aqueous solution by UV irradiation at 253.7 nm.

The effect of dissolved oxygen on the photodecomposition of monochloramine (7.5 < pH < 10) and dichloramine (pH = 3.7 +/- 0.2) at 253.7 nm has been investigated. The kinetic study shows that the rate of photodecomposition of monochloramine is about two times faster in the absence of oxygen than in the presence of oxygen, is not significantly affected by pH and by the presence of hydroxyl radical scavengers (hydrogenocarbonate ion and tert-butanol). The apparent quantum yields of photodecomposition of monochloramine at 253.7 nm ([NH(2)Cl](0) approximately 1.5-2 mM, epsilon(253.7 nm) = 371 M(-1) cm(-1)) were equal to 0.28 +/- 0.03 and 0.54 +/- 0.03 mol E(-1) in oxygenated-saturated and in oxygen-free solutions, respectively. The photodecomposition rates or the apparent quantum yields of photodecomposition of dichloramine ([NHCl(2)](0) approximately 1.5-2 mM, pH = 3.7 +/- 0.2) in oxygen-free and in oxygen-saturated solutions were quite identical (Phi = 0.82 +/- 0.08 mol E(-1); epsilon(253.7 nm) = 126 M(-1) cm(-1)). Under O(2) saturation, UV irradiation of NH(2)Cl leads to the formation of nitrite ( approximately 0.37 mol/mol of NH(2)Cl decomposed), nitrate ( approximately 0.073 mol/mol) and does not form ammonia (<0.01 mol/mol). In oxygen-free solutions, monochloramine decomposes to form ammonia ( approximately 0.37 mol/mol). Photodecomposition of dichloramine did not lead to significant amounts of nitrite and nitrate in the presence and in the absence of oxygen. The nitrogen mass balances also indicate the formation of other nitrogen species (probably N(2) and/or N(2)O) during the photodecomposition of monochloramine and dichloramine by UV irradiation at 253.7 nm.

Monochloramination of resorcinol: mechanism and kinetic modeling.

The kinetics of monochloramination of resorcinol, 4-chlororesorcinol, and 4,6-dichlororesorcinol have been investigated over the pH range of 5-12, at 23 +/- 2 degrees C. Monochloramine solutions were prepared with ammonia-to-chlorine ratios (N/Cl) ranging from 1.08 to 31 mol/mol. Under conditions that minimize free chlorine reactions (N/Cl > 2 mol/mol), the apparent second-order rate constants of monochloramination of resorcinol compounds show a maximum at pH values between 8.6 and 10.2. The intrinsic second-order rate constants for the reaction of monochloramine with the acid-base forms of the dihydroxybenzenes (Ar(OH)(2), Ar(OH)O(-), and Ar(O(-))(2)) were calculated from the apparent second-order rate constants. The stoichiometric coefficients for the formation of 4-chlororesorcinol by monochloramination of resorcinol and 4,6-dichlororesorcinol by monochloramination of 4-chlororesorcinol were found to be equal to 0.66 +/- 0.05 and 0.25 +/- 0.02 mol/mol, respectively at pH 8.6. A kinetic model that incorporates reactions of free chlorine and monochloramine with the different acid-base forms of resorcinol compounds simulated well the initial rates of degradation of resorcinol compounds and was useful to evaluate the contribution of free chlorine reactions to the overall rates of degradation of resorcinol at low N/Cl ratios.