Innovative Membrane-Based Catalytic Process for Environmentally Friendly Synthesis of Oxygenates

Synthesis of liquid oxygenates from light alkanes (C₁--C₃) is achieved in a multifunctional three-phase catalytic membrane reactor (3PCMR) operating under mild conditions (T_R, 80-120 °C; P_R, 140 kPa). The features of superacid catalytic membranes mediated by the Meⁿ⁺/H₂O₂ Fenton system in activating C₁-C₃ alkanes are presented. The effect of operating conditions ([H₂O₂], [Meⁿ⁺]) on the catalyst activity is outlined. A general reaction pathway accounting for the activation of the CH bond of the alkane molecule on the superacid sites and the subsequent reaction of the activated alkane with primary reactive intermediates, generated from the Meⁿ⁺/H₂O₂ system, is proposed. The suitability of the 3PCMR in enabling simultaneous reaction and product separation is discussed.     

From single crystals to supported nanoparticles in experimental and theoretical studies of H2 oxidation over platinum metals (Pt, Pd): Intermediates, surface waves and spillover

The present paper reviews our investigations concerning the mechanism of H₂ + O₂ reaction on the metal surfaces (Pt, Pd) at different structures: single crystals (Pt(1 1 1), Pt(1 0 0), Pd(1 1 0)); microcrystals (Pt tips); and nanoparticles (Pd–Ti³⁺/TiO₂). Field electron microscopy (FEM), field ion microscopy (FIM), high-resolution electron energy loss spectroscopy (HREELS), XPS, UPS, work function (WF), TDS and temperature-programmed reaction (TPR) methods have been applied to study the kinetics of H₂ oxidation on a nanolevel. The adsorption of both O₂ and H₂ and several dissociative products (H_ads, O_ads, OH_ads) was studied by HREELS. Using the DFT technique the equilibrium states and stretching vibrations of H, O, OH, H₂O, adsorbed on the Pt(1 1 1) surface, have been calculated depending on the surrounding of the metal atoms. Sharp tips of Pt, several hundreds angstroms in radius, were used to perform in situ investigations of the dynamic surface processes. The FEM and FIM studies on the Pt-tip surface demonstrate that the self-oscillations and waves propagations are connected with periodic changes in the surface structure of nanoplane (1 0 0)-(hex) ↔ (1 × 1), varying the catalytic property of metal. The role of defects (Ti³⁺-□_O) in the adsorption centers formation, their stabilization by the palladium nanoparticles, and then the defects participation in H₂ + O₂ steady-state reaction over Pd–Ti³⁺/TiO₂ surface have been studied by XPS, UPS and photodesorption techniques (PhDS). This reaction seems to involve the “protonate” hydrogen atoms (H⁺/TiO_x) as a result of spillover effect: diffusion of H_ads atoms from Pd particles on a TiO_x surface. The comprehensive study of H₂, O₂ adsorption and H₂ + O₂ reaction in a row: single crystals → tips → nanoparticles has shown the same nature of active centers over these metal surfaces.     

Hydrogen transfer and activation of propane and methane on ZSM5-based catalysts

Hydrogen exchange between undeuterated and perdeuterated light alkanes (CD₄-C₃H₈, C₃D₈-C₃H₈) occurs on H-ZSM5 and on Ga- and Zn-exchanged H-ZSM5 at 773 K. Alkane conversion to aromatics occurs much more slowly because it is limited by rate of disposal of H-atoms formed in C-H scission steps and not by C-H bond activation. Kinetic coupling of these C-H activation steps with hydrogen transfer to acceptor sites (Ga ⁿ⁺, Zn ^m+) and ultimately to stoichiometric hydrogen acceptors (H⁺, CO₂,O₂, CO) often increases alkane activation rates and the selectivity to unsaturated products. Reactions of¹³ CH₄/C₃H₈ mixtures at 773 K lead only to unlabelled alkane, alkene, and aromatic products, even though exchange between CD₄ and C₃H₈ occurs at these reaction conditions. This suggests that the non-oxidative conversion of CH₄ to higher hydrocarbons on solid acids is limited by elementary steps that occur after the initial activation of C-H bonds.     

Similarity and differences in the oxidative dehydrogenation of C2–C4 alkanes over nano-sized VOx species using N2O and O2

The effect of O₂ and N₂O on alkane reactivity and olefin selectivity in the oxidative dehydrogenation of ethane, propane, n-butane, and iso-butane over highly dispersed VO_x species (0.79 V/nm²) supported on MCM-41 has been systematically investigated. For all the reactions studied, olefin selectivity was significantly improved upon replacing O₂ with N₂O. This is due to suppressing CO_x formation in the presence of N₂O. The most significant improving effect of N₂O was observed for iso-butane dehydrogenation: S(iso-butene) was ca. 67% at X(iso-butane) of 25%.Possible origins of the superior performance of N₂O were derived from transient experiments using ¹⁸O₂ traces. ¹⁸O¹⁶O species were detected in ¹⁸O₂ and ¹⁸O₂–C₃H₈ transient experiments indicating reversible oxygen chemisorption. In the presence of alkanes, the isotopic heteroexchange of O₂ strongly increased. Based on the distribution of labeled oxygen in CO_x and in O₂ as well as on the increased CO_x formation in sequential O₂–C₃H₈ experiments, it is suggested that non-lattice oxygen species (possibly of a bi-atomic nature) originating from O₂ are non-selective ones and responsible for CO_x formation. These species are not formed from N₂O.     

Infrared chemiluminescence study of CO produced by partial oxidation of butane on platinum

The selective formation of CO and H₂ was observed by a molecular-beam catalytic reaction betweenn-C₄H₁₀ and O₂ on a Pt surface from around 1000 to 1500 K. The infrared emission of the product CO desorbed from the surface showed that the CO molecules are vibrationally substantially excited but rotationally very cool (rotational temperature;T _R = 360 K). The present molecular-beam study showed that CO and H₂ were formed directly from the hydrocarbon and O₂ without involving formation of CO₂ and H₂O as primary products. The implications of these results are discussed for the partial oxidation of methane (and other alkanes) to synthesis gas using practical supported metal catalysts.     

Influence of nature/concentration of halide promoters and oxidation state on the direct oxidation of H2 to H2O2 over Pd/ZrO2 catalysts in aqueous acidic medium

The nature/concentration of halide promoters and influence of the Pd oxidation state on the promoted reaction system has been investigated on the direct H₂O₂ process over a 2.5 wt.% Pd/ZrO₂ catalyst in an aqueous acidic reaction medium. The oxidation state of Pd had a profound influence on the H₂O₂ synthesis process. Interestingly, the nature of the halide determined the magnitude/type of influence the Pd oxidation state exerted on the overall process. While the effect of the oxidation state on the H₂O₂ yields was large for the reaction systems containing F⁻ or no halide, the effect was significantly smaller for the reaction systems containing Br⁻ and Cl⁻. The nature of the halide also strongly influenced the H₂O₂ synthesis process. Br⁻ strongly enhanced the H₂O₂ yields, while F⁻ had a negative influence on the H₂O₂ yields. The ability of the halides to enhance the H₂O₂ process was found to strongly depend on its propensity to suppress the secondary H₂O₂ decomposition reaction. The influence of Br⁻ and Cl⁻concentration studies revealed that the optimum halide concentration for the direct H₂O₂ synthesis process was dependent on the nature of the halide. While the maximum in H₂O₂ yields for the Br⁻ containing reaction medium corresponded to a concentration of ∼0.9 mmol/dm³ (KBr) the maximum for the Cl⁻ containing solution was obtained at ∼1.5 mmol/dm³ (KCl). Such knowledge is crucial from the viewpoint of optimization (catalyst/reaction system screening studies) of the direct H₂O₂ process. The qualitative trends (H₂O₂ selectivity/yield) observed in case of the incorporated halide catalysts were similar to those observed with halides in reaction medium over the Pd/ZrO₂ catalyst.     

Mechanism in chlorine-enhanced Pd catalyst for H2O2 in situ synthesis in electro-Fenton system

Palladium-based catalysts have been widely employed in the electro-Fenton process for in situ generation of H₂O₂. However, the process is still far from being practical on a large scale. In this work, a series of Cl_xFePd/γ-Al₂O₃/Al catalysts were prepared by a three-step-impregnation method. They exhibited excellent activity in H₂O₂ in situ synthesis and high efficiency in phenol degradation. The characterization results showed that Cl could assist in increasing the content of Pd⁰ and reducing the isoelectric point of catalysts, which led to the drastic promotion in the synthesis of H₂O₂. Theoretical calculations further demonstrated that Cl doping could facilitate the main reaction in H₂O₂ synthesis, as well as inhibit side reactions such as dissociation of the O O bond. Furthermore, kinetic models were proposed and fitted. A plausible reaction mechanism as well as degradation pathways were elaborated based on electron spin resonance and gas chromatography–mass spectrometry results. These findings illustrate the value of palladium-based Cl_xFePd/γ-Al₂O₃/Al catalysts for their application in the electro-Fenton process.     

Application of a C6‐OH of chitosan immobilized cyclodextrin derivates on an electrochemical H2O2 biosensor

Biosensor detecting techniques have attracted much attention in the content determination of H₂O₂, which has been used illegally as a food additive. An electrochemical biosensing membrane for the detection of H₂O₂ was developed with C6‐OH of chitosan immobilized cyclodextrin derivates (6‐CD–CTS), which possessed a high cyclodextrin loading capacity (2.12 × 10^?4 mol/g), as the carrier. The biosensor was prepared through the inclusion of ferrocene as the electron mediator in a hydrophobic cavity of cyclodextrin and crosslinking catalase (CAT) to 2‐NH₂ of 6‐CD–CTS. The ferrocene‐included complex was evaluated by ultraviolet–visible spectrophotometry and thermogravimetric analysis. Its electrochemical behavior was also studied. The impact of the reaction conditions on the CAT immobilization capacity was evaluated. When previous membrane was used to detect the concentration of H₂O₂ (C_H2O2), we found that the catalysis of CAT and the signal amplification of ferrocene had a major impact on the cyclic voltammograms. The optimal working pH of the modified electrode was 7.0. The peak current (I) had a linear relationship with the H₂O₂ concentration (CH₂O₂) in the range 1.0 × 10^?4 to 1.0 × 10^?3 mol/L. The linear regression equation was I = 0.00475C_H2O2 ? 0.03025. The detection limit was 10^?6 mol/L. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41499.     

Hydrogen Spillover in Ga2O3–Pd/SiO2 Catalysts for Methanol Synthesis from CO2/H2

The hydrogenation of CO₂ was investigated on Ga₂O₃-promoted Pd/SiO₂ catalyts and mechanical mixtures of Ga₂O₃/SiO₂ and Pd/SiO₂ catalysts (H₂/CO₂ = 3; P = 3.0 MPa; T = 523 K). By means of the latter it was possible to demonstrate that atomic hydrogen, H_s, can be generated by Pd⁰ far from Ga₂O₃, and move (spill-over) there to reach the other reactive species (formates) and complete the reaction cycle. The reaction results indicate that (as also evidenced by in situ FTIR) the Ga₂O₃-Pd/SiO₂ catalyst works as a true bi-functional system. The metal-promoter intimacy is not decisive in terms of the catalytic chemistry of the system, but the closeness between the Pd crystallites and the Ga₂O₃ surface patches boost the activity, owing to a minimized effort in the H_s supply to the latter.     

Direct Oxidation of H2 to H2O2 and Decomposition of H2O2 Over Oxidized and Reduced Pd-Containing Zeolite Catalysts in Acidic Medium

Both the conversion and H₂O₂ selectivity (or yield) in direct oxidation of H₂-to-H₂O₂ (using 1.7 mol% H₂ in O₂ as a feed) and also the H₂O₂ decomposition over zeolite (viz. H-ZSM-5, H-GaAlMFI and H- ) supported palladium catalysts (at 22 °C and atmospheric pressure) are strongly influenced by the zeolite support and its fluorination, the reaction medium (viz. pure water, 0.016 M or 1.0 M NaCl solution or 0.016 M H₂SO₄, HCl, HNO₃, H₃PO₄ and HClO₄), and also by the form of palladium (Pd⁰ or PdO). The oxidized (PdO-containing) catalysts are active for the H₂-to-H₂O₂ conversion and show very poor activity for the H₂O₂ decomposition. However, the reduced (Pd⁰-containing) catalysts show higher H₂ conversion activity but with no selectivity for H₂O₂, and also show much higher H₂O₂ decomposition activity. No direct correlation is observed between the H₂-to-H₂O₂ conversion activity (or H₂O₂ selectivity) and the Pd dispersion or surface acidity of the catalysts. Higher H₂O₂ yield and lower H₂O₂ decomposition activity are, however, obtained when the non-acidic reaction medium (water with or without NaCl) is replaced by the acidic one.     

Treatment of Jewelry Manufacturing Effluent Containing Cyanide Using Ozone-Based Photochemical Advanced Oxidation Processes

This article considers Advanced Oxidation Processes involving O₃, O₃/UV, O₃/H₂O₂/UV, and H₂O₂/UV to destroy cyanide in jewelry manufacturing wastewaters. All experiments were performed in a semibatch reactor. The results showed that total cyanide can be reduced with different reaction rates, and the decrease of total cyanide can be described by pseudo–first-order kinetics. The reaction was performed under different pH values and H₂O₂ dosages to find the optimal conditions for the oxidation processes. The ozonation process destroyed total cyanide faster at a pH = 12, whereas ozonation combined with H₂O₂ and/or UV destroyed cyanide faster at a pH =10. The total cyanide destruction rate in the UV/H₂O₂ (700 mg/L) treatment was the highest among all studied processes, with removal efficiencies of 99% for CN^?, 99% for COD and 99% for TOC.     

Aqueous-Phase Reforming of Ethylene Glycol Over Supported Platinum Catalysts

Aqueous-phase reforming of 10 wt% ethylene glycol solutions was studied at temperatures of 483 and 498 K over Pt-black and Pt supported on TiO₂, Al₂O₃, carbon, SiO₂, SiO₂-Al₂O₃, ZrO₂, CeO₂, and ZnO. High activity for the production of H₂ by aqueous-phase reforming was observed over Pt-black and over Pt supported on TiO₂, carbon, and Al₂O₃ (i.e., turnover frequencies near 8-15 min^-1 at 498 K); moderate catalytic activity for the production of hydrogen is demonstrated by Pt supported on SiO₂-Al₂O₃ and ZrO₂ (turnover frequencies near 5 min^-1); and lower catalytic activity is exhibited by Pt supported on CeO₂, ZnO, and SiO₂ (H₂ turnover frequencies lower than about 2 min^-1). Pt supported on Al₂O₃, and to a lesser extent ZrO₂, exhibits high selectivity for production of H₂ and CO₂ from aqueous-phase reforming of ethylene glycol. In contrast, Pt supported on carbon, TiO₂, SiO₂-Al₂O₃ and Pt-black produce measurable amounts of gaseous alkanes and liquid-phase compounds that would lead to alkanes at higher conversions (e.g., ethanol, acetic acid, acetaldehyde). The total rate of formation of these byproducts is about 1-3 min^-1 at 498 K. An important bifunctional route for the formation of liquid-phase alkane-precursor compounds over less selective catalysts involves dehydration reactions on the catalyst support (or in the aqueous reforming solution) followed by hydrogenation reactions on Pt.     

Oxygen Isotope Transport Properties of Yttria‐Stabilized Zirconia (YSZ) in O2‐ and H2O‐Containing Atmospheres

Oxygen isotope exchange experiments, H₂¹⁸O/H₂¹⁶O (”wet” anneals) and ¹⁸O₂/¹⁶O₂ (”dry” anneals), were performed on single crystal samples of yttria‐stabilized zirconia (YSZ) at a temperature of T = 1073 K with subsequent determination of the oxygen isotope profiles in the solid by time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Such experiments yielded oxygen tracer diffusion coefficients (D*) and oxygen tracer surface exchange coefficients (k*), from both the polished (smooth) and unpolished (rough) sides of single crystal samples, as a function of water partial pressure pH₂O and oxygen partial pressure pO₂. Isothermal values of D* were found to depend on neither pO₂ nor pH₂O (nor surface roughness). Isothermal values of k*, in contrast, displayed a strong dependence on pO₂ or pH₂O; k*_wet was, in addition, 2–3 orders of magnitude higher than k*_dry. Surprisingly, surface roughness had little effect on k*_wet, whereas rough surfaces exhibited much higher k*_dry values than smooth surfaces. Data for k*_wet obtained as a function of temperature at pH₂O = 18 mbar show a change in activation enthalpy at T ≈ 973 K. The behavior of k* is discussed in terms of surface composition, surface area and surface reaction mechanisms.     

In situ controlled electrochemical promotion of catalyst surfaces: Pd-catalysed ethylene oxidation

The catalytic activity of polycrystalline Pd films deposited on 8 mol% Y₂O₃-stabilized–ZrO₂ (YSZ), an O^2–-conductor, can be altered reversibly by varying the potential of the Pd catalyst film via the effect of nonfaradaic electrochemical modification of catalytic activity (NEMCA) or electrochemical promotion. The complete oxidation of ethylene was investigated as a model reaction in the temperature range 290–360 °C and atmospheric total pressure. The rate of C₂H₄ oxidation can be reversibly enhanced by up to 45% by supplying O^2– to the catalyst via positive current application. The steady-state rate change is typically 10³–10⁴ times larger than the steady-state rate I/2F of electrochemical supply or removal of promoting oxide ions. The observed behaviour is discussed on the basis of previous NEMCA studies and the mechanism of the reaction.     

An Efficient Strategy for the Production of Epoxidized Oils: Natural Deep Eutectic Solvent-Based Enzymatic Epoxidation

Poor H₂O₂-resistance by enzymes is a key bottleneck in the epoxidation process of oil by enzymatic methods. In this study, the stability of three lipases, from Aspergillus oryzae lipase (AOL), Aspergillus fumigatus lipase B (AflB), and marine Janibacter (MAJ1), in the presence of H₂O₂ was evaluated in different types of natural deep eutectic solvents (NADES). This stability was strengthened significantly in the NADES compared to the buffer. Specifically, AOL retained 84.7% of its initial activity in the presence of choline chloride/sorbitol (1:1 M ratio) and 3 mol L⁻¹ H₂O₂ after 24 h incubation at 40°C. In addition, the two-phase epoxidation process was optimized with AOL in ChCl/sorbitol to reach up to 96.8% conversion under the optimized conditions (molar ratio of octanoic acid/H₂O₂/C=C-bonds = 0.3:1.5:1, enzyme loading of 15 U g⁻¹ of soybean oil, ChCl/sorbitol content of 70.0% of the weight of hydrophilic phase, and reaction temperature of 50°C). Moreover, the lipase dispersed in NADES retained approximately 66% of its initial activity after being used for seven batch cycles. Overall, NADES-based enzymatic epoxidation is a feasible and promising strategy for the synthesis of epoxidized oils.     

Direct H2-to-H2O2 oxidation over highly active/selective Br–F–Pd/Al2O3 catalyst in aqueous acidic medium: Influence of process conditions on the H2O2 formation

The influence of the O₂/H₂ mole ratio in the gaseous feed and also those of other reaction conditions [viz. concentration of H₃PO₄ (0–5 mol/dm³), temperature (5–50 °C), gas (H₂ and O₂) space velocity (5.8–23.4 h^?1) and reaction time (0.1–8 h)] on the H₂O₂ formation in the H₂-to-H₂O₂ oxidation over the Br(1 wt%)–F(1 wt%)–Pd(5 wt%)/Al₂O₃ catalyst in an aqueous acidic (H₃PO₄) medium have been thoroughly investigated. The effects of the O₂/H₂ ratio, reaction temperature and acid concentration on the destruction of H₂O₂ by its decomposition and/or hydrogenation reactions over the catalyst in the acidic reaction medium have also been studied. The net H₂O₂ formation (H₂O₂ yield) over the catalyst passed through a maximum with increasing the acid concentration, the temperature or the O₂/H₂ feed ratio. However, it decreased markedly with increasing the gas space velocity or the reaction period. The H₂O₂ decomposition and hydrogenation activities of the catalyst increased appreciably with increasing the reaction temperature and decreased with increasing the acid concentration. The H₂O₂ destruction during the H₂-to-H₂O₂ oxidation increased with increasing the concentration of H₂ (relative to that of O₂) due to the increased H₂O₂ hydrogenation rate over the catalyst. The net H₂O₂ formation in the H₂-to-H₂O₂ oxidation decreased sharply with increasing the initial amount of H₂O₂ present in the reaction mixture. The presence of H₂O₂ and the higher H₂/O₂ ratios have detrimental effects on the net formation of H₂O₂.     

The issue of selectivity in the direct synthesis of H2O2 from H2 and O2: the role of the catalyst in relation to the kinetics of reaction

The kinetic behavior in the direct synthesis of H₂O₂ with Pd–Me (Me = Ag, Pt) catalysts prepared by depositing the noble metals by electroless plating deposition (EPD) or deposition–precipitation (DP) methods on α-Al₂O₃ asymmetric ceramic membrane with or without a further surface coating by a carbon thin layer is reported. The effect of the second metal with respect to Pd-only catalysts considerably depends on the presence of the carbon layer on the membrane support. Several factors in the preparation of these membranes as well as the reaction conditions (temperature, concentration of Br⁻, pH) determine the selectivity in H₂O₂ formation, influencing the rate of the consecutive reduction of H₂O₂ (which is faster with respect to H₂O₂ decomposition on the metal surface) and/or of direct H₂ + O₂ conversion to H₂O. Defective Pd sites are indicated to be responsible for the two unselective reactions leading to water formation (parallel and consecutive to H₂O₂ formation), but the rate constants of the two reactions are differently influenced from the catalytic membrane characteristics. Increasing the noble metal loading on the membrane not only increases the productivity to H₂O₂, but also the selectivity, due to the formation of larger, less defective, Pd particles.     

Single- and double-stage catalytic preferential CO oxidation in H2-rich stream over an α-Fe2O3-promoted CuO–CeO2 catalyst

Single- and double-stage catalytic preferential CO oxidation (CO-PrOx) over-Fe₂O₃-promoted CuO–CeO₂ in a H₂-rich stream has been investigated in this work. The catalyst was prepared by the urea-nitrate combustion method and was characterized by X-ray diffractometer (XRD), X-ray fluorescence (XRF), Brunauer–Emmet–Teller (BET), transmission electron microscope (TEM), and scanning electron microscope (SEM). The catalytic activity tests were carried out in the temperature range of 50–225 °C under atmospheric pressure. The results of the single-stage reaction indicated that complete CO oxidation was obtained when operating at a O₂/CO ratio of 1.5, W/F ratio of 0.36 g s/cm³, and at a reaction temperature of 175 °C. At these conditions, H₂ consumption in the oxidation was estimated at 58.4%. Applying the same conditions to the double-stage reaction, complete CO oxidation was found and H₂ consumption in the oxidation was reduced about 4.9%. When decreasing the double-stage reaction temperature to 150 °C, the results elucidated that CO could be converted to CO₂ completely while H₂ consumption in the oxidation was further reduced to 33.5%. A temperature blocking 2² factorial design has been used to describe the importance of the factors influencing the catalytic activity. The factorial design was according to the experimental results. When adding CO₂ and H₂O in feed, reduction of CO conversion for single- and double-stage reaction is obtained due to a blocking of CO₂ and H₂O at a catalytic active site. Comparing CO conversion obtained when operating with/without CO₂ and H₂O in feed for single- and double-stage reaction, less reduction is achieved when operating in double-stage reaction.     

The mechanism of electrodeposition of acrylic resin on aluminium

A mechanism for the electrodeposition of acrylic resin on aluminium is proposed, based on experimental studies of acid value, anodic gas evaluation and anodic film resistance. The mechanism can be expressed as Alf Al³⁺ + 3e 2Al³⁺ + 3H₂Of Al₂O₃ + 6H⁺ 2Al³⁺ + 6H₂Of 2Al(OH)₃ + 6H⁺ H⁺ + RCOC^– f RCOOH. This is different from the mechanism for zinc and steel, where it is metal ions from anodic dissolution which neutralize the macro-ions and cause a deposit on the anode surface.     

Comparison of Ozone and Hydroxyl Radical-Induced Oxidation of Chlorinated Hydrocarbons in Water

The efficiency of ozonation and advanced oxidation processes such as ozone/UV, ozone/H₂O₂ and H₂O₂/UV was assessed for chlorinated hydrocarbons using a closed batch-type system. 1,1-Dichloropropene (DCPE), trichloroethylene (TCE), 1-chloropentane (CPA), and 1,2-dichloroethane (DCA) were used as model compounds.

The direct reaction between substrates and ozone predominated at lower pH, which resulted in the efficient oxidation of the olefin, DCPE. At higher pH, ozonation resulted in more efficient oxidation of the chlorinated alkanes, with a corresponding decrease in the efficiency of DCPE oxidation. Consistent results were observed for ozone/H₂O₂ and ozone/UV treatment. Due to slow UV-induced decomposition of H₂O₂, the process using H₂O₂/UV (254 nm) resulted in very slow oxidation of all four compounds.

The total ozone requirement to achieve a given degree of elimination (to 37% of the original concentration), δ0.37, was used to assess the combined effects of the direct and indirect reactions for different types of waters.