Second-order Rate Constants For Reactions Research Articles

How does pH influence ferrate(VI) oxidation of fluoroquinolone antibiotics?

• Kinetic model of fluoroquinolones oxidation by Fe(VI) was built at pH 3.0–9.0. • Reactive sites and main reactions were proposed based on theoretical calculation. • Fe VI , Fe V , and Fe IV were primary reactive species at both alkaline and acidic pH. • HO was yielded via Fenton or Fenton-like process at acidic pH in Fe(VI) oxidation. This study investigated the impact of pH on the efficiency of ferrate (Fe(VI), K 2 FeO 4 ) toward fluoroquinolone antibiotics, built kinetic models of Fe(VI) oxidation, and elucidated the involved active species during Fe(VI) oxidation at acidic and alkaline conditions. It was found that the second-order reaction rate constants ( k app , M −1 s −1 ) of Fe(VI) with three fluoroquinolone antibiotics (i.e., enroxacin, ofloxacin, and norfloxacin) were strongly dependent on pH, and k app reached its maximum at pH about 6.5. The reactions between HFeO 4 - /H 2 FeO 4 and neutral/protonated fluoroquinolone antibiotics (X and XH + ) were the major ones. Moreover, the reactive species were identified as high-valent iron species, i.e., Fe(VI), Fe(V), and Fe(IV), in alkaline solution, while hydroxyl radicals was generated through Fenton or Fenton-like processes at acidic condition with limited contribution.

Photodegradation of propranolol in surface waters: An important role of carbonate radical and enhancing toxicity phenomenon

Antihypertensive propranolol (PRO) is frequently detected in surface waters and has adverse effects on aquatic organisms. In this study, its photochemical fate in surface water with the aspect of kinetics, products and toxicity were investigated employing steady-state photochemistry experiments and ecotoxicity tests. The results showed that photodegradation of PRO was enhanced in river water than that in phosphate buffer where dissolved organic matter (DOM), NO3−, and HCO3− played important roles. DOM accelerated the photodegradation mainly through generation of excited triplet-state DOM while NO3− played dual roles in the photodegradation. The reaction between excited triplet-state PRO and HCO3− can generate carbonate radical (CO3·-) to promote the photodegradation. The second-order reaction rate constant between PRO and CO3·- was determined to be (3.4 ± 0.8) × 108 M−1 s−1. Eight photodegradation products were identified in the studied river water sample. Finally, the toxicity evaluated by Vibrio fischeri increased after photodegradation and three photodegradation products were responsible for the increasing toxicity, which was concluded from the significant correlation between toxicity parameters and quantity of the photodegradation products.

Reaction kinetics of dissolved black carbon with hydroxyl radical, sulfate radical and reactive chlorine radicals

As an important component of dissolved organic matter (DOM), dissolved black carbon (DBC) which is characterized of abundant aromatic and oxygen-containing functional groups, is widely distributed in aquatic environments. Its presence may hinder the oxidation of organic micro-pollutants during advanced oxidation processes (AOPs) via free radicals scavenging effect. However, the second-order reaction rate constants of DBC with different free radicals including hydroxyl radical (OH•), sulfate radical (SO4•-), reactive chlorine radicals (RCR) are unknown and the relationship between the chemical composition of DBC and the second-order reaction rate constants during different AOPs (UV/H2O2, UV/PDS, UV/Chlorine) is also unclear. In this study, a plant-derived DBC was extracted from wheat biochar and fractionated according to molecular weight (i.e., <10 k, <3 k, and < 1 k Da). The second order rate constants of DBC reaction with different free radicals were determined by competitive kinetic method. Besides, the chemical composition of DBC was revealed by ultraviolet-visible (UV–Vis) spectroscopy, fluorescence excitation-emission-matrix (EEM) spectroscopy Fourier Transform Infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with statistical analysis. The results showed that the second-order rate constants decreased as the molecular weight increased. For the <1 k Da DBC, the kDBC-OH•, kDBC-SO4•-−, kDBC-RCR were (1.83 ± 0.06) × 104, (7.60 ± 0.21) × 103, and (1.71 ± 0.13) × 104 L·mgC−1·s−1, which were 1.98, 2.19, 1.43 times of that for the <10 k Da fraction and 1.38, 1.36, 1.24 times of that for the <3 k Da fraction in UV/H2O2, UV/PDS and UV/Chlorine processes. In addition, the results of chemical composition analysis showed that DBC mainly contained humic substances and was rich in O-containing functional groups such as CO. The second order reaction rate constants of DBC with different free radicals decreased with increasing the molecular weight of DBC due to the more aggregated structure of the small molecules that the inner carbon of DBC was not easily exposed to free radicals.

Kinetics and Mechanism of Degradation of Reactive Radical-Mediated Probe Compounds by the UV/Chlorine Process: Theoretical Calculation and Experimental Verification.

The UV/chlorine process, by combining chlorination with UV irradiation, has been recently considered as a highly efficient advanced oxidation process (AOP) technology in water treatment. Nitrobenzene (NB), benzoic acid (BA), and p-chlorobenzoic acid (pCBA) are widely used as model probe compounds in the UV/chlorine system to calculate the second-order rate constants of the specific radical reaction with target contaminates by a competitive kinetics method. A comprehensive understanding of probe compounds’ reaction mechanism with reactive radicals is critical for investigation of the UV/chlorine reaction system. Here, we evaluated the radical-mediated reaction kinetics and mechanism of NB, BA, and pCBA in the UV/chlorine process using theoretical calculations and experimental studies. The main reactive radicals •OH, •ClO, and •Cl in the UV/chlorine process for the initial reaction with NB, BA, and pCBA can be explained by H-abstraction and addition pathways. The ΔE0,≠ values for the •OH reaction with NB, BA, and pCBA were in the range of 5.0–8.0, 3.7–8.2, and 3.4–8.2 kcal mol–1, respectively. The ΔE0,≠ values for •ClO and •Cl reactions with these three probe compounds were higher than those of •OH, indicating slower •ClO- and •Cl-initiated reactions than that of the •OH-initiated reaction. The theoretically calculated radical-mediated reaction kinetic rate constants (kCPC) for NB, BA, and pCBA were 4.58 × 10–3, 1.28 × 10–2, and 1.6 × 10–2 s–1, respectively, which was consistent with the experimentally determined pseudo-first-order rate constant (kCPRR) in the UV/chlorine process. Interestingly, theoretical calculations showed that •ClO and •Cl played an important role in subsequent reactions of NB-OH radicals, converting to hydroxylated and chlorinated products, which were further confirmed by experimental products’ identification. The findings from this study indicated that quantum chemistry calculations provide an effective means to investigate the reaction kinetics and mechanism of chemicals in the UV/chlorine process.

Linear Relationship between Temperature and the Apparent Reaction Rate Constant of Hydroxyl Radical with 4-chlorobenzoic Acid

ABSTRACT 4-Chlorobenzoic acid (p-CBA) is frequently used as a hydroxyl radical (HO·) probe substance in studies of ozonation and advanced oxidation processes. However, the temperature dependence of the reaction between HO· and p-CBA remains unclear. In this context, we identified the relationship between temperature ( T , K) and the apparent second-order reaction rate constant of HO· with p- CBA ( k H O ⋅ , p − C B A T , M−1 s−1): 10 10 . They were measured by a novel competitive method using 2-methylpropan-2-ol (tert-butyl alcohol) as a reference substance in the range of 1.0–40.0℃. The linear regression equation was more appropriate than the exponential regression equation to express this relationship. More generally, our simulation shows that the linear regression equation can be more accurate than the exponential regression equation to express the relationship between temperature and apparent reaction rate constants of HO.

The Determination and Prediction of the Second-Order Rate Constants for Reactions between Excited Triplet-State Dom and Selected Ppcps

The Determination and Prediction of the Second-Order Rate Constants for Reactions between Excited Triplet-State Dom and Selected Ppcps

Kinetic Study on the Reactivity of Azanone (HNO) toward Cyclic C-Nucleophiles.

Azanone (HNO) is an elusive electrophilic reactive nitrogen species of growing pharmacological and biological significance. Here, we present a comparative kinetic study of HNO reactivity toward selected cyclic C-nucleophiles under aqueous conditions at pH 7.4. We applied the competition kinetics method, which is based on the use of a fluorescein-derived boronate probe FlBA and two parallel HNO reactions: with the studied scavenger or with O2 (k = 1.8 × 104 M−1s−1). We determined the second-order rate constants of HNO reactions with 13 structurally diverse C-nucleophiles (k = 33–20,000 M−1s−1). The results show that the reactivity of HNO toward C-nucleophiles depends strongly on the structure of the scavenger. The data are supported with quantum mechanical calculations. A comprehensive discussion of the HNO reaction with C-nucleophiles is provided.

Reaction kinetics and degradation efficiency of halogenated methylparabens during ozonation and UV/H2O2 treatment of drinking water and wastewater effluent

This study investigated the reaction kinetics and degradation efficiency of methylparaben and its halogenated products (Cl-, Br-, Cl,Cl-, Br,Cl-, and Br,Br-methylparabens) during ozonation and UV254/H2O2 treatment. Second-order rate constants for reactions of the parabens with ozone and •OH were kO3 = 107 – 108 M−1 s−1 and k•OH = (2.3 – 4.3)× 109 M−1 s−1 at pH 7. Species-specific kO3 values of the protonated and deprotonated parabens were closely related to phenol ring substituent effects via quantitative structure-activity relationships with other substituted phenols. The UV photolysis rate of the parabens [kUV = (2.4 − 7.2)× 10−4 cm2 mJ−1] depended on the halogenation state of the paraben and solution pH, from which species-specific quantum yields were also determined. In simulated treatments of drinking water and wastewater effluent, the parabens were efficiently eliminated during ozonation, requiring a specific ozone dose of > 0.26 gO3/gDOC for > 97% degradation. During UV/H2O2 treatment with 10 mg L−1 H2O2, the degradation levels were > 90% at a UV fluence of 2000 mJ cm−2, except for Cl,Cl-methylparaben. Kinetic models based on the obtained reaction kinetic parameters could successfully predict the degradation levels of the parabens. Overall, ozonation and UV/H2O2 were effective in controlling parabens and their halogenated products during advanced water treatment.

Oxidation of pyrazolone pharmaceuticals by peracetic acid: Kinetics, mechanism and genetic toxicity variations

Peracetic acid (PAA) oxidation is an emerging technology in water disinfection and purification. This study evaluated the oxidation of three pyrazolone pharmaceuticals (i.e., Aminopyrine (AMP), Antipyrine (ANT), and Isopropylphenazone (PRP) by PAA. Experimental results showed that PAA exhibited structure selectivity to the above three pharmaceuticals and oxidized AMP with the highest reactivity. The degradation kinetics of AMP was investigated by calculating the apparent second-order rate constants (kapp) under different initial pH. Through kinetic simulation, the second-order rate constants of elementary reactions between AMP (i.e., neutral (AMP0) and protonated (AMP+) species) with PAA (i.e., neutral (PAA0) and anionic (PAA−) species) were obtained to be 0.34 ± 0.077 M−1 s−1(k”AMP+, PAA0), 0.89 ± 0.091 M−1 s−1(k”AMP0, PAA-) and 5.94 ± 0.142 M−1 s−1(k”AMP0, PAA0), respectively. The PAA could oxidize AMP via electrophilic attack, and the degradation site of AMP was confirmed to be the central nitrogen of –N(CH3)2 with the highest relative electrophilicity (sk-/sk+, 48.8614) by Density Functional Theory (DFT) calculation. The intermediates/products of AMP degradation were identified by high-performance liquid chromatography-mass spectrometry (LC-MS/MS), and the transformation pathways of AMP during PAA oxidation were inferred to be hydroxylation, demethylation, and CC cleavage. The genetic toxicity of AMP contaminated water could be reduced after PAA oxidation, which was evaluated by the micronucleus test of Vicia faba root tips.

Photodegradation and ozonation of ibuprofen derivatives in the water environment: Kinetics approach and assessment of mineralization and biodegradability

This article presents the results of studies on the degradation of ibuprofen transformation products: 1-hydroxyibuprofen (1OHIBF), 4-ethylbenzaldehyde (4EBA), 1-[4-(2-methylpropyl)phenyl]ethan-1-ol (MPPE) in water. To the best of our knowledge, this is the first paper where the ozonation and photodegradation (VIS and UV photolysis, degradation in H2O2/UV system, photosensitized oxidation) of 1OHIBF, 4EBA and MPPE are reported. The processes were performed in demineralized and natural river water. The influence of various reaction parameters on the removal degree was checked. Both, photolysis under VIS light and photosensitized oxidation of target compounds are very low-efficient processes. Ozonation and degradation in H2O2/UV system are effective methods for ibuprofen derivatives degradation. Components present in river water reduced removal degree of investigated compounds during ozonation and degradation in H2O2/UV system. The biodegradability assessment using the Average Oxidation State (AOS) and COD/TOC ratio proved the formation of more oxidized by-products during both processes. The determined second-order rate constants for ozone reaction with 1OHIBF, 4EBA and MPPE are 0.1 ± 0.01, 10.95 ± 1.36 and 3.04 ± 0.33 M−1 s−1, respectively. The calculated reaction rate constants of hydroxyl radicals with MPPE, 4EBA and 1OHIBF are 3.57 × 109, 6.83 × 109 and 1.06 × 109 M−1 s−1, respectively.

Photodegradation of benzophenones sensitized by nitrite

Benzophenone UV filters (BPs) are a group of contaminants of emerging concern due to their widespread occurrence and adverse effects on aquatic ecosystems. In this study, the transformation of BPs by nitrite sensitized photodegradation was comprehensively investigated. OH and NO2 generated by nitrite photolysis reacted with BPs, forming hydroxylated and nitrated products, respectively. Kinetic modeling revealed that the steady-state concentrations of NO2 were approximately six orders of magnitude higher than those of OH in the UV/nitrite process, although the second-order rate constants of NO2 reactions with BPs were six orders of magnitude lower. With the increase in nitrite concentration, BPs degradation was accelerated, and the contribution of NO2 increased as well. At initial nitrite concentration of 10 μM, the contributions of OH and NO2 to the degradation of 2,4-dihydroxybenzophenone (BP1) were 66.1% and 21.5%, respectively. However, NO2 only contributed a tiny fraction to the degradation of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (BP4), due to the presence of an electron-withdrawing sulfonate group in the molecule. Natural organic matter (NOM) inhibited the nitrite sensitized degradation of BPs, due to light screening and radical scavenging effects. This study suggests that BPs can be effectively transformed in sunlit waters in the presence of nitrite, leading to nitrated products.

Photochemical oxidation of o-dichlorobenzene in aqueous solution by hydroxyl radicals from nitrous acid

The mechanism and kinetic parameters of the photochemical reaction of o-dichlorobenzene (o-DCB) in the presence of nitrite were studied by steady-state irradiation and laser flash photolysis. The degradation efficiency of o-DCB was observed to be influenced by N(III) (H2ONO+, HONO, NO2−) concentration, initial concentration of o-DCB and pH value. The hydroxyl radicals generated by the photolysis of N(III) attacked the benzene ring of o-DCB to form an o-DCB-OH adduct with the second-order reaction rate constant of (2.69 ± 0.3) × 109 L mol−1 s−1. Subsequently, the o-DCB-OH adduct reacts with molecular oxygen, NO2, H2ONO+ and HONO with rate constants of (1.28 ± 0.3) × 108 L mol−1 s−1, (1.5 ± 0.4) × 108 L mol−1 s−1, (1.3 ± 0.2) × 107 L mol−1 s−1 and (1.0 ± 0.3) × 107 L mol−1 s−1, respectively. The main products of the OH-initiated reaction of o-DCB were identified by gas chromatograph and mass spectrometer (GC–MS) to be o-chlorophenol, 2-chloro-3-nitrophenol, 1,2-dichloronitrobenzene, 2,3-dichlorophenol, 2,3-dichloro-1,4-benzoquinone and 2,3-dichloro-4-nitrophenol and the reaction mechanism leading to these products is discussed.

Rate Constants and Mechanisms for Reactions of Bromine Radicals with Trace Organic Contaminants.

Bromine radicals can pose great impacts on the photochemical transformation of trace organic contaminants in natural and engineered waters. However, the reaction kinetics and mechanisms involved are barely known. In this work, second-order reaction rate constants with Br• and Br2•- were determined for 70 common trace organic contaminants and for 17 model compounds using laser flash photolysis and steady-state competition kinetics. The kBr• values ranged from <108 to (2.86 ± 0.31) × 1010 M-1 s-1 and the kBr2•- values from <105 to (1.18 ± 0.09) × 109 M-1 s-1 at pH 7.0. Six quantitative structure-activity relationships were developed, which allow predicting additional unknown kBr• and kBr2•- values. Single-electron transfer was shown to be a favored pathway for the reactions of Br• and Br2•- with trace organic contaminants, and this was supported by transient spectroscopy and quantum chemical calculations. This study is essential in advancing the scientific understanding of halogen radical-involved chemistry in contaminant transformation.

Modeling degradation kinetics of gemfibrozil and naproxen in the UV/chlorine system: Roles of reactive species and effects of water matrix

The UV/chlorine system has been regarded as an efficient oxidation technology for the removal of aqueous micropollutants. However, the roles of the possible radical species for this system on the elimination under environmentally relevant conditions/real waters were still largely unknown. Herein, the specific roles of radical species in the UV/chlorine oxidation degradation of gemfibrozil and naproxen as representative micropollutants were quantified by a steady-state kinetic prediction model considering the effects of water matrices. Overall, the model predicted results are consistent with the experimental data well. •OH and reactive chlorine species (RCS, such as Cl•, ClO•, and Cl2•−) contributions to gemfibrozil and naproxen degradation were water matrix specific. In pure water, both primary reactive species (i.e., •OH and Cl•) and secondary species ClO• dominated gemfibrozil and naproxen degradation, and their individual and the sum of the contributions to degradation rates reduced with pH increase of from 5 to 9. In the presence of Cl−, we found that Cl2•− and in particular ClO• were responsible for the enhanced degradation with increasing Cl− concentrations due to the considerable ClO• reactivity of gemfibrozil (1.93 × 109 M−1 s−1) and naproxen (9.24 × 109 M−1 s−1) and the rapid transformation of Cl2•− to ClO•. The presence of HCO3− notably facilitated the degradation in the UV/chlorine process because of the generation of CO3•−. CO3•− showed high reactivity with gemfibrozil and naproxen corresponding to respective second-order reaction rate constants of 2.45 × 107 and 3.50 × 107 M−1 s−1. Dissolved organic matter induced obvious scavenging for •OH, Cl•, and ClO• and greatly retarded the degradation. The constructed model considering the effects of above water matrix has successfully predicted the oxidation degradation kinetics in real waters, and both •OH and CO3•− are the predominant reactive species in the degradation. This study is helpful for comprehensive understanding the roles of possible radical species in micropollutant removal by UV/chlorine oxidation under real water matrix.

Photochemical reaction of superoxide radicals with 1-naphthol

The photochemical reactions between 1-naphthol (1-NP) and the superoxide anion radical (O2•–) were investigated in detail by using 365 nm UV irradiation. The results showed that the conversion rate of 1-NP decreased with the increase of the initial concentration of 1-NP, whereas by increasing the pH and riboflavin concentration, the photochemical reaction was accelerated. The second-order reaction rate constant was estimated to be (3.64 ± 0.17) × 108 L mol−1s−1. The major photolysis products identified by using gas chromatography – mass spectrometry (GC–MS) were 1,4-naphquinone and 2,3-epoxyresin-2,3-dihydro-1,4-naphquinone, and their reaction pathways were also discussed. An atmospheric model showed that both the bulk water reaction and the heterogeneous surface reaction deserve attention in atmospheric aqueous chemistry.

Mass-transfer kinetics of CO2 in a hybrid choline-2-pyrrolidine-carboxylic acid/polyethylene glycol/water absorbent

Understanding the mass-transfer kinetics of CO2 in novel hybrid absorbents with physical and chemical contributions is essential for process design and evaluation. In this study, the liquid-side mass-transfer coefficients (kL) and second-order reaction rate constants (k2) of CO2 in hybrid absorbents (namely, choline-2-pyrrolidine-carboxylic acid salt/polyethylene glycol/water ([Cho][Pro]/PEG200/H2O)) were determined. The kL values for the hybrid absorbents were obtained from the CO2 diffusion coefficients (DCO2) and the kL values in PEG200/H2O. The DCO2 value was calculated from the density and viscosity of the hybrid absorbents, whereas the kL values in PEG200/H2O were measured experimentally. The k2 values of CO2 in the hybrid absorbents were estimated according to the reaction mechanism, the enhancement factor, and the kL values, and compared with those of other commercialized absorbents. The results showed that 30 wt% [Cho][Pro] + 70 wt% H2O had the highest kL and k2 values at atmospheric pressure, whereas the values of kL and k2 of CO2 in 30 wt% [Cho][Pro]/H2O + PEG200 were comparable to those in diethanolamine aqueous and amino-functionalized ILs. The hybrid absorbent of [Cho][Pro]/PEG200/H2O could be promising for CO2 separation considering its thermodynamic and kinetic properties.

Study of Antithyroid and Antioxidant Properties of Cysteine, Glutathione, and Methionine by Spectrophotometry and High Performance Liquid Chromatography

The antithyroid properties of sulfur-containing amino acids cysteine and methionine and glutathione tripeptide are studied by evaluating the kinetic and thermodynamic parameters of analyte interaction anionic iodine complexes ( $${\text{I}}_{{\text{3}}}^{ - }$$ and I2Cl–).The rate constant of the second-order reaction between cysteine and triiodide is the maximum rate constant, comparable to the rate constants of physiological processes. The antioxidant activity of cysteine and glutathione is estimated by the kinetic method with the spectrophotometric control of the reaction rate using the second-order reaction rate constant with the chromogen radical 2,2'-diphenyl-1-picrylhydrazyl (DPPH) and the reaction half-life in alcoholic media. The antioxidant properties of cysteine and glutathione, manifested in the reaction with DPPH, were used to develop a simple and sensitive method for their quantitative determination using a pseudo-first-order rate constant. The study of the reaction of analytes with a chromogen radical made it possible to evaluate their antiradical activity by spectrophotometry analysis, supplemented with HPLC.

Aqueous picloram degradation by hydroxyl radicals: Unveiling mechanism, kinetics, and ecotoxicity through experimental and theoretical approaches

Pesticides are chemical compounds widely used to combat pests in crops, and they thus play a key role in agricultural production. However, due to their persistence in aquatic environments, even at low concentrations, their use has been considered an environmental problem and caused concern regarding the adverse effects on human health. This paper reports, for the first time, the mechanisms, kinetics, and an evaluation of the toxicity of picloram degradation initiated by OH radicals in the aqueous environment using quantum chemistry and computational toxicology calculations. The rate constants are calculated using a combination of formulations derived from the Transition State Theory in a realistic temperature range (250–310 K). The results indicate that the two favorable pathways (R1 and R5) of OH -based reactions occur by addition to the pyridine ring. The calculated rate constant at 298 K is compared with the overall second-order reaction rate constant, quantified herein experimentally via the competition kinetics method and data available in the literature showing an excellent agreement. The toxicity assessment and a photolysis study provide important information: i) picloram and the majority of degradation products are estimated as harmful; however, ii) these compounds can suffer photolysis in sunlight. The results of the present study can help understand the mechanism of picloram, also providing important clues regarding risk assessment in aquatic environments as well as novel experimental information.

Measurement of the Absorption Rates of Carbon Dioxide in Aqueous Solutions of Piperazine and Sulfolane Using the Stopped-flow Technique

With the accelaration of the exploitation of natural gas reservoirs, the efficient removal of contaminants such as CO2, H2S, RSH, and COS is becoming of critical importance. In recent years, there is a growing interest in using amine blends or mixed solvents instead of a single amine for gas sweetening processes. Mixed solvents composed of a chemical solvent and a physical solvent take advantage of the benefits of both physical and chemical absorptions. The study of the absorption kinetics of the mixed solvent are necessary for designing and optimizing the process for removal of CO2 from natural gas, synthesis gas, or reformer gas. As a physical solvent, Sulfolane has excellent stability and low corrosiveness, in addition to a high capability for CO2 absorption. Sulfinol is a comercially successful process used in more than 200 plants and based on the use of Sulfolane as a physical solvent and either Diisopropanolamine (DIPA) or Methyldiethanolamine (MDEA) as chemical solvents. Mixed Sulfolane-based solvents have recently been proposed for post-combustion CO2 capture. In this study, the reaction kinetics of carbon dioxide (CO2) in aqueous solutions of aqueous piperazine (PZ) and an aqueous mixed solvent of (PZ + Sulfolane) were measured using the stopped flow technique resulting in the meaurement of observed pseudo-first-order rate constants (k0) allowing for the calculation of the second-order reaction rate constants (k2). The experiments were carried out over) concentration ranges of (10 to 60) for PZ, and (10 to 40, 10 to 200) (mol/m3) for PZ and Sulfolane, respectively and temperatures ranging from (298.15 to 313.15) K. Results show that the kinetic rates of the mixed solvent (PZ + Sulfolane + Water) were higher than those in aqueous PZ at all temperatures. The reaction kinetics in aqueous mixed solents of (PZ + Sulfolane) in reaction with CO2 increase with increasing temperature and concentration. The Termolecular mechanisms correlated the aqueous mixed systems of (PZ + Sulfolane) successfully. The reaction kinetics increased with the increase in temperature and concentration. The addition of Sulfolane to aqueous PZ resulted in increased absorption rates. Thus, the mixed solvent of PZ, Sulfolane and water can be considered an attractive alternative to aqueous amines for the enhancement of CO2 capture.

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.