Numerical simulation of the thermal destruction of some chlorinated C1 and C2 hydrocarbons

We have numerically modeled the breakdown of small quantities of several chlorinated hydrocarbons (CH3Cl, CH2Cl2, CHCl3, CCl4, C2H3Cl, and C2H5Cl) in a lean mixture of combustion products between 800 and 1480 K. This simulates the fate of poorly atomized waste in a liquid-injection incinerator. Kinetics calculations were performed using the CHEMKIN and SENKIN programs, with a reaction mechanism that was developed at Louisiana State University to model flat-flame burner experiments. A 99.99-percent destruction efficiency was attained in one second at temperatures ranging from 1280 to 960 K, with CCl4 requiring the highest temperature for destruction and C2H5Cl the lowest. For all compounds except C2H5Cl, there was a range of temperatures at which byproducts accounted for several percent of the elemental chlorine at the outlet. The more heavily chlorinated compounds formed more byproducts even though the amount of elemental chlorine was the same in all cases. The sensitivity of results to residence time, equivalence ratio, temperature profile, and the presence of additional chlorine, was examined for the case of CHCl3.     

Direct VUV photolysis of chlorinated methanes and their mixtures in an oxygen stream using an ozone producing low-pressure mercury vapour lamp

The gas-phase photooxidations of CCl(4), CHCl(3), CH(2)Cl(2) and their binary mixtures in an O(2) stream were studied in a flow reactor under various experimental conditions using a low-pressure mercury lamp as light source covered with a high-purity silica sleeve being used. The 184.9 nm VUV irradiation emitted is responsible for the Cl-C bond rupture in the chlorinated methanes and for the formation of O(3) from O(2). The rate of degradation of H-containing chlorinated methanes increased sharply on increase of their initial concentrations, most probably of a (*)Cl chain reaction, as indicated by the increase in the molar ratio of the amount of HCl formed to the amount of H-containing target substance decomposed. The experimental results suggested that the further transformations of the radicals and products formed play an important role as (*)Cl sources, causing a considerably higher rate of decomposition of the H-containing target substances. In a humidified O(2) stream, the (*)OH formed opens up another route for oxidation of the target substances. Thus, the rates of degradation of CH(2)Cl(2) and CHCl(3) increased on increase of the relative humidity, whereas the water vapour had no effect at all on the decomposition of CCl(4). At the same time, competition occurs between (*)Cl or (*)OH for reactions with the target substance. The photooxidation of binary mixtures was investigated too. The addition of CCl(4) or CHCl(3) to CH(2)Cl(2) strongly increased its degradation rate. The addition of CH(2)Cl(2) did not have a considerable effect on the rate of degradation of CHCl(3).     

Extraction of chlorinated aliphatic hydrocarbons from groundwater at micromolar concentrations for isotopic analysis of chlorine.

A method is described for near-quantitative extraction of micromolar concentrations of chlorinated aliphatic hydrocarbons (CAHs) from water for determination of chlorine (Cl) isotope ratios. A low pressure, carrier-gas procedure of extraction was proven to be applicable to CH2Cl2, CCl4, C2H2Cl2, and C2HCl3. The pH of the water was adjusted with NaOH to prevent extraction of CO2 from air and/or dissolved inorganic carbonate species. Recoveries of CAH samples (approximately 15 mumol), added to and extracted from approximately 340 ml of water, averaged approximately 96%. Average changes in the delta 37Cl values of the CAHs, attributable to the extraction process, were -0.01 +/- 0.06@1000. Significant isotopic fractionation of Cl was measured during partial extraction of C2CHCl3 from water, indicating that near-quantitative extraction is required for reliable stable Cl isotope analysis of CAHs. This method is also suitable for the extraction of dissolved CAH for gas chromatography-combustion-isotope ratio mass spectrometric measurements of hydrogen and carbon.     

Gas-phase reaction of CCl2F2 (CFC-12) with methane

Gas-phase reaction of CFC-12 (CCl2F2) with methane was carried out in a plug flow reactor over the temperature range of 873-1123 K. The major organic halocarbons formed during the reaction were C2F4, C2H2F2, CHClF2, CH3Cl, C3H2F6 and CCl3F. The formation of all products except C2H2F2 decreased with temperature, while the selectivity to C2H2F2 (difluoroethylene) increased with temperature and reached approximately 80% at 1123 K. Under these reaction conditions, methane acts as hydrogen and carbon source, resulting in the formation of an unsaturated C2 hydrofluorocarbon from two C1 precursors.     

Mineralization of organic micropollutants (homologous alcohols and phenols) in water by vacuum-UV-oxidation (H2O-VUV) with an incoherent xenon-excimer lamp at 172 nm

Twenty different organic micropollutants (for example C1-C8 homologous alcohols and some phenols) in aqueous solution were subjected to vacuum-UV-oxidation (H2O-VUV) within a xenon-excimer flow-through photoreactor. The incoherent xenon-excimer lamp used exhibited an emission maximum at 172 nm. At this wavelength water is efficiently photolyzed with formation of hydrogen atoms and of highly oxidative hydroxyl radicals. The short lived hydroxyl radicals initiate a series of complex interrelated radical reactions that lead finally to the mineralization of the organic material dissolved in water. The efficiency of the total organic carbon (TOC) diminution is dependent on the nature of the organic substrate treated. For example, in the series of homologous alcohols the substrate methanol is mineralized faster than 1-octanol by a factor of 2.7 under identical conditions of VUV treatment and with similar initial TOC content of the water ranging between 40 and 50 ppm.     

Formation and decomposition of chloroaromatic compounds in chlorine-containing benzene/oxygen flames

Premixed chlorine-containing, fuel-rich, low-pressure benzene/oxygen flames were analysed for the formation of (oxygenated) chloroaromatic compounds and their radicals by means of the condensation/radical-scavenging method (Hausmann, M., Homann, K.-H., 1995. Ber. Busenges. Phys. Chem. 99, 853-862). Several chlorinated organic compounds (methyl chloride, t-butyl chloride, chlorobenzene, chloroform) were used as additives within a maximum concentration of 10% of total fuel. Product identification and quantification were performed by GC/MS. The extent of formation of chloroaromatic compounds in these flames was largest in the cases of chlorobenzene and chloroform as additives. For chlorobenzene, 12 different chloroaromatics could be analysed in between C7H7Cl and C12H9Cl. Their formation is mainly due to conversion of initial chlorobenzene into substituted or oxidised derivatives, or growth products. Additional chlorination of aromatics is shown to be of minor importance in chlorobenzene-containing flames. Three isomeric (o/m/p) scavenging products could be identified for the chlorophenyl radical. In the chloroform case, 15 chloroaromatics could be analysed in between C6H5Cl and C14H9Cl. The weak C-Cl bond in chloroform is responsible for the high extent of chloroaromatics formation, either by Cl abstraction from the additive or by chlorination reactions via Cl radicals. Additionally, specific pathways to (di)chloroaromatics and chlorinated fulvene-type structures are outlined via CHCl2 and CCl2 radicals.     

Effect of biogenic iron species and copper ions on the reduction of carbon tetrachloride under iron-reducing conditions

In this study, the cell-mediated and abiotic reduction of carbon tetrachloride (CCl(4)) by biogenic iron species produced from the reductive dissolution of ferrihydrite in the presence of Geobacter sulfurreducens and copper ions (Cu(II)) were investigated. 9,10-Anthraquinone-2,6-disulfonate (AQDS), serving as a surrogate of natural organic matters and an electron shuttling compound, was added to enhance the efficiency of biological reduction of the solid Fe(III) minerals. G. sulfurreducens drove the reduction of CCl(4), primarily through the formation of biogenic surface-bound iron species produced from the reductive dissolution of ferrihydrite, in the presence of 10microM AQDS. The pseudo-first-order rate constant (k(obsCT)) for CCl(4) transformation in the presence of ferrihydrite was 3.0 times higher than that resulting from the use of G. sulfurreducens alone. Addition of 0.5mM Cu(II) slightly inhibited both the growth of G. sulfurreducens and the production of biogenic Fe(II). However, the k(obsCT) values for CCl(4) transformation in ferrihydrite suspensions containing G. sulfurreducens and 0.3-0.5mM Cu(II) were 2.1-4.2 times higher than that observed in the absence of Cu(II). X-Ray powder diffraction analysis indicated that the added Cu(II) reacted with the biogenic Fe(II) ions to produce catalytic cuprous ions (Cu(I)) and secondary iron oxide minerals such as magnetite and goethite, resulting in accelerating the chemical transformation efficiency and rate of CCl(4) under iron-reducing conditions.     

Chlorinated hydrocarbons in Scots pine needles in northern Britain

Concentrations of 4 chlorinated hydrocarbons, C2H3Cl3 (1,1,1-trichloroethane), CCl4 (tetrachloromethane), C2HCl3 (trichloroethene) and C2Cl4 (tetrachloroethene) have been measured in needles of Scots pine (Pinus sylvestris L.) growing close to two industrial sites and in a rural area in northern Britain. Pentane extracts of pine needles sampled over 14 months were analysed using gas chromatography with electron capture detection. Geometric mean concentrations were not significantly different among the sites, with values (in ng g(-1) dry weight) of 7-15 for C2H3Cl3, 3.2-6.5 for CCl4, 70-240 for C2HCl3 and 11-26 for C2Cl4. There was no evidence of accumulation with needle age, but more exposed sites (e.g. those higher in the canopy) showed significantly larger concentrations. The influence of possible local sources could not be detected.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

Decomposition of halogenated methanes in oxygen-free gas mixtures by the use of a silent electric discharge

A silent electric discharge was applied to decompose halogenated methanes including CCl4, CHCl3, CFCl3, CF2Cl2 and CF3Cl, in argon-containing gas mixtures. The decompositions of the target compounds were studied in static reactors at a fixed electric field and room temperature. The reaction products were analyzed by FT-IR spectroscopy, gas chromatography and UV spectrophotometry. The results demonstrated, that the radical-type decomposition of chlorofluoromethanes led to products formed by realignment of the halogen atoms. The decomposition of CCl4 was faster than that of the cholorofluoromethanes, and produced perchloroethane and chlorine. CHCl3 exhibited the highest decomposition rate and produced a large variety of products.     

Biodegradation of chlorinated solvents in a water unsaturated topsoil

In order to investigate topsoils as potential sinks for chlorinated solvents from the atmosphere, the degradation of trichloromethane (CHCl(3)), 1,1,1-trichloroethane (CH(3)CCl(3)), tetrachloromethane (CCl(4)), trichloroethene (C(2)HCl(3)) and tetrachloroethene (C(2)Cl(4)) was studied in anoxic laboratory experiments designed to simulate denitrifying conditions in water unsaturated topsoil. Active denitrification was demonstrated by measuring the release of 15N in N(2) to the headspace from added 15N labeled nitrate. The degradation of chlorinated aliphatic compounds was followed by measuring their concentrations in the headspace above the soil.The headspace concentrations of all the chlorinated solvents except CH(3)CCl(3) were significantly (P相似文献   

A laser flash photolysis study of the decay of SO4- and Cl2- radical anions in the presence of Cl- in aqueous solutions

The rate constant for the reaction of sulphate radical (SO4-) with Cl- has been determined using laser photolysis, at 248 nm, of peroxodisulphate anions to produce the radicals and time resolved optical absorption of the transient species (at 450 or 480 nm for SO4- and 350 nm for Cl2-) for the kinetic determinations. The experiments were performed, in the absence of added sulphate, as a function of temperature and ionic strength and yielded (at an ionic strength of 0.0157 M): kIV = (9.90+/-0.16) x 10(9) exp((-7.12+/-2.0) kJ mol(-1)/RT) M(-1) s(-1), where the errors reflect the 2sigma statistical error. This reaction produces Cl2-, the formation and decay of which were also monitored allowing a determination of the rate constant of its second-order self-recombination reaction which gave k = (6.50+/-1.40) x 10(8) M(-1) s(-1) at 293 K and zero ionic strength.     

Degradation of aqueous carbon tetrachloride by nanoscale zerovalent copper on a cation resin

Nanoscale zerovalent copper supported on a cation resin was successfully synthesized to enhance the removal of carbon tetrachloride (CCl(4)) from contaminated water. The use of the cation resin as a support prevents the reduction of surface area due to agglomeration of nanoscale zerovalent copper particles. Moreover, the cation resin recycles the copper ions resulting from the reaction between CCl(4) and Cu(0) by simultaneous ion exchange. The decline in the amount of CCl(4) in aqueous solution results from the combined effects of degradation by nanoscale zerovalent copper and sorption by the cation resin; thus the amount of CCl(4) both in aqueous solution and sorbed onto the resin were measured. The pseudo-first-order rate constant normalized by the surface-area and the mass concentration of nanoscale zerovalent copper (k(SA)) was 2.1+/-0.1 x 10(-2)lh(-1)m(-2), approximately twenty times that of commercial powdered zerovalent copper (0.04 mm). Due to the exchange between Cu(2+) and the strongly acidic ions (H(+) or Na(+)), the pH was between 3 and 4 in unbuffered solution and Cu(2+) at the concentration of less than 0.1 mg l(-1) was measured after the dechlorination reaction. In the above-ground application, resin as a support would facilitate the development of a process that could be designed for convenient emplacement and regeneration of porous reductive medium.     

Direct VUV photolysis of chlorinated methanes and their mixtures in a nitrogen stream

The gas-phase decomposition of CCl(4), CHCl(3) and CH(2)Cl(2) and their binary mixtures was studied in a flow-type reactor in a nitrogen gas stream, using a low-pressure mercury vapour lamp covered with a high-purity silica quartz sleeve. The 184.9 nm vacuum-ultraviolet (VUV) light emitted is able to rupture the C-Cl bond in these target substances. For H-containing compounds, the decomposition takes place not only by direct photolysis, but also by H abstraction by .Cl formed during the direct photolysis of the target substances. The relative contributions of direct photolysis and .Cl-sensitized reactions to the decomposition were estimated at different initial concentrations. The addition of CCl(4) to CHCl(3) or CH(2)Cl(2) increased their decomposition rates via increase of the .Cl concentration, whereas the addition of CH(2)Cl(2) to CHCl(3) decreased its degradation rate, suggesting that CH(2)Cl(2) acts as a .Cl radical scavenger. The variation of the product distribution confirms the effect of the composition of the irradiated gas mixtures on the relative contributions of .Cl-sensitized reactions and direct photolysis.     

The role of organic ligands in ferrous-induced photochemical degradation of 2,4-dichlorophenoxyacetic acid

Recent studies have shown that hydrogen peroxide is generated in a ferrioxalate-induced photoreductive reaction, but information about the effect of organic ligands on the photochemical behaviour of ferrous species is limited. The degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by a ferrous-catalyzed oxidation in the presence of various ligands such as formate, citrate, malelate, oxalate, and ethylenediaminetetra-acetic acid (EDTA) was studied. The experiments were conducted under either dark or irradiated (350n m) conditions. Forty-two percent and 34% of 2,4-D were removed by the Fe(2+)/oxalate/UV and Fe(2+)/citrate/UV processes, respectively, after 30 min of reaction and oxidative intermediates were obtained in both cases. The presence of hydroxylated intermediates suggests that 2,4-D may be attacked by hydroxyl radicals, which are the products of the photo-Fenton-like reaction. As such, hydrogen peroxide was produced by the photolysis of ferrous oxalate or ferrous citrate, referred to hereafter as photogenerated H(2)O(2). As expected, the total removal percentage of 2,4-D jumped to 97% when 1mM of hydrogen peroxide (so-called spiked H(2)O(2)) was externally added to the reaction vessel to initiate the Fe(2+)/oxalate/UV process. Therefore, the treatment of 2,4-D by the Fe(2+)/oxalate/H(2)O(2)/UV system can be operated in two steps: the photolysis of ferrous oxalate first, followed by adding the spiked H(2)O(2) sometime after the commencement of the reaction. A two-phase model has been developed to describe this tandem ferrous-catalyzed photooxidation, which would help to achieve the mineralization of 2,4-D.     

Mineralization of the biocide chloroxylenol by electrochemical advanced oxidation processes

Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.     

Degradation of tris(1-chloro-2-propanyl) phosphate by the synergistic effect of persulfate and zero-valent iron during a mechanochemical process

This study revealed a dual pathway for the degradation of tris(1-chloro-2-propanyl) phosphate (TCPP) by zero-valent iron (ZVI) and persulfate as co-milling agents in a mechanochemical (MC) process. Persulfate was activated with ZVI to degrade TCPP in a planetary ball mill. After milling for 2 h, 96.5% of the TCPP was degraded with the release of 63.16, 50.39, and 42.01% of the Cl^?, SO₄^2?, and PO₄^3?, respectively. In the first degradation pathway, persulfate was activated with ZVI to produce hydroxyl (·OH) radicals, and ZVI is oxidized to Fe(II) and Fe(III). A substitution reaction occurred as a result of the attack of ·OH on the P–O–C bonds, leading to the successive breakage of the three P–O–C bonds in TCPP to produce PO₄^3?. In the second pathway, a C–Cl bond in part of the TCPP molecule was oxidized by SO₄·^? to carbonyl and carboxyl groups. The P–O–C bonds continued to react with ·OH to produce PO₄^3?. Finally, the intermediate organochloride products were further reductively dechlorinated by ZVI. However, the synergistic effect of the oxidation (·OH and SO₄·^?) and the reduction reaction (ZVI) did not completely degrade TCPP to CO₂, resulting in a low mineralization rate (35.87%). Moreover, the intermediate products still showed the toxicities in LD₅₀ and developmental toxicant. In addition, the method was applied for the degradation of TCPP in soil, and high degradations (>?83.83%) were achieved in different types of soils.

     

Effect of Fe0 quantity on the efficiency of integrated microbial-Fe0 treatment processes

Batch experiments were conducted with different reaction systems to investigate how the treatment efficiency of integrated microbial-Fe0 processes is affected by the amount of Fe0 added. Abiotic experiments with hexavalent chromium and carbon tetrachloride mixtures corroborated that different pollutants could compete for reactive sites on the iron surface, which would hinder specific degradation rates when the available Fe0 surface area is relatively small (e.g., 11 m(2) l(-1)). In such cases, reductive precipitation of chromium could occlude reactive sites and significantly inhibit removal efficiency. Microbial participation in the cleanup process was also influenced by the amount of Fe0 added. Increasing the Fe0 dose (and thus the available surface area) had a stimulatory effect possibly due to a higher production of cathodic H2, which can be used as electron donor for reductive biotransformation of many pollutants. However, high Fe0 doses had an inhibitory effect due to a corrosion-induced increase in pH beyond the optimum range of the bacteria. This suggest that there may be a system-specific, optimum quantity of Fe0 that satisfies availability requirements to preclude contaminant competition for reactive sites and biological requirements for H2 production while minimizing inhibitory increases in pH. Results also confirmed extensive RDX mineralization in bioaugmented (but not in abiotic) Fe0 systems, and support the notion that permeable reactive iron barriers performance might be enhanced by the participation of some microorganisms.     

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics,reaction intermediates,and toxicity assessment

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄ of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺ and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄ ⁺, NO₃ ^?, and SO₄ ^2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.     

Oxidation of trichloroethene over metal oxide catalysts: kinetic studies and correlation with adsorption properties

The performance of bulk chromium oxide is compared with that of a Mn commercial catalyst for the deep oxidation of trichloroethene (1000-2500ppmv, 55h(-1) space velocity) in air, in dry and wet (20000ppm of H(2)O) conditions, in terms of activity, selectivity and stability. Chromium oxide was found to be more active (on a catalyst weight basis), however its activity decreases continuously with time on stream. The presence of water increases its stability, the Mn catalyst showing the opposite behaviour. The effect of water on the Cr catalyst can be explained according to the Deacon equilibrium, as the presence of water tends to decrease the Cl(2) concentration, assumed to be responsible of the catalyst deactivation. Regarding to the selectivity, the Mn catalyst yields C(2)Cl(4), CCl(4) and CHCl(3) as organochlorinated by-products, whereas chromium oxide produces only trace amounts of CCl(4). Simple power-law kinetics expressions (first-order for Mn and zero-order for Cr) provide fairly good fits for the evolution of the conversion with the temperature. Furthermore, the kinetic behaviour of chromium oxide can be represented with a Langmuir-Hinshelwood model taking into account the chlorine inhibitory effect.