Destruction of 2,4-Dichlorophenol in Water Solution Using a Combined Process of Sorption and Plasma Exposure to DBD

The results of studies of the decomposition of 2,4-dichlorophenol (2,4-DCP) in its aqueous solution under the action of atmospheric pressure DBD in an oxygen flow are presented. A new reactor design was used in which the discharge zone was filled with a sorbent (diatomite). It was found that the kinetics of decomposition obeys a first-order kinetic equation for the concentration of 2,4-DCP. The presence of an adsorbent significantly improves the parameters of the decomposition process. Decomposition rates, rate constants and energy efficiency are doubled. So, at a specific discharge power of 1.8 W/cm³ in the presence of a sorbent, the rate constant was ~1 s^?1, and without it, ~0.5 s^?1. The energy efficiency was 0.031 and 0.016 molecules per 100 eV, respectively. The parameters of the treated solution are improved in terms of its potential toxicity. The concentrations of the main decomposition products (aldehydes, carboxylic acids) in the presence of a sorbent are significantly less than without it. This is due to an increase in the rate of conversion of these products into carbon dioxide molecules. It was also shown that the decomposition of one 2,4-DCP molecule leads to the formation of two chloride ions in solution, and the ozone formed in the discharge does not significantly affect the destruction process.

     

A Study of Sulfonol Decomposition in Water Solutions Under the Action of Dielectric Barrier Discharge in the Presence of Different Heterogeneous Catalysts

The decomposition kinetics of sulfonol (surfactant) in water solutions as well as the formation kinetics of decomposition products under the action of an oxygen dielectric barrier discharge (DBD) at atmospheric pressure in the presence or absence of TiO₂, NiO and Ag₂O catalysts in the plasma zone was studied. The DBD discharge was shown to have high decomposition efficiency (phenol-up to 98%, sulfonol-up to 80%). In a plasma-catalytic hybrid process, the efficiency of organic substances decomposition was higher than efficiency for the DBD treatment without catalyst. The catalysts application resulted in a change in the ratio and yield of decomposition products.     

Destruction of 2,4 Dichlorophenol in an Atmospheric Pressure Dielectric Barrier Discharge in Oxygen

The processes of degradation of 2,4-dichlorophenol (2,4-DCP) under the action of atmospheric pressure of dielectric barrier discharge (DBD) in oxygen were studied. It was shown that the degradation of 2,4-DCP proceeds efficiently. Degree of decomposition reaches 90%. The degradation kinetics of 2,4-DCP obeys the formal first-order kinetic law on concentration of 2,4-DCP. The effective rate constants depend weakly on the experimental conditions and are equal to ~0.2 s^?1. Based on experimental data, the energy efficiency of decomposition of 2,4-DCP was determined. Depending on the conditions, the energy efficiency was in the range of (8–90) × 10^?3 molecules per 100 eV. The composition of the products was studied by gas chromatography (GC), gas chromatography–mass spectrometry (GC–MS), energy-dispersive X-ray spectroscopy (EDX), attenuated total reflection-fourier transform infrared (ATR-FTIR) spectroscopy, electron spin resonance (ESR) spectroscopy and UV/Visible spectroscopy. It was shown that about ~20% of 2,4-DCP is converted to CO₂, while the other part forms an organic film on the reactor wall. The substance formed is close to the carboxylic acids in chemical composition and exhibits electrical conductivity and paramagnetic properties. Almost all of the chlorine contained in the 2,4-DCP is released into the gas phase. The active species of the afterglow react with liquid hexane, forming the products of its oxidation. Some assumptions regarding the pathway of the process are discussed.     

A Novel Dielectric-Barrier-Discharge Loop Reactor for Cyanide Water Treatment

A novel dielectric-barrier-discharge (DBD) loop reactor was designed for the efficient degradation of cyanide anion (CN^?) in water. The circulation of cyanide water as a falling film through plasma gas discharge zone enhanced gas–liquid mass and energy transfer and induced formation of H₂O₂ which was associated with the efficient destruction of CN^?. It was observed that among different discharge gases, the CN^? degradation rate decreased in the order of Ar > air > H₂/air mixture. Depending on discharge voltage, the treatment time for complete removal of 100 ppm CN^? in this DBD loop reactor is in the range 120–300 min. The dose of Cu²⁺ catalyst in combination with in situ production of H₂O₂ enhanced the destruction of CN^? apparently in this DBD loop reactor. The treatment time for complete degradation of 100 ppm CN^? decreased from 180 min with Ar DBD discharge alone to 40 min with 40 mg/L dose of Cu²⁺ ion in water, making it an efficient means to degrade cyanide water.     

Application of Dielectric Barrier Discharge for Waste Water Purification

This study considers treatment of real city rain sewage under the action of an oxygen dielectric barrier discharge (DBD) at atmospheric pressure in the presence or absence of TiO₂ catalyst in the plasma zone. The DBD discharge has been shown to have high decomposition efficiency (up to 98%) for oil hydrocarbons, phenols and synthetic surfactants. The discharge action resulted in the decrease of heavy metal (Pb, Cd, Fe, Mn) content as well. In a plasma-catalytic hybrid process, the efficiency of organic substances decomposition was higher than efficiency for the DBD treatment without catalyst.     

Kinetics and Mechanism of Cr(VI) Reduction in a Water Cathode Induced by Atmospheric Pressure DC Discharge in Air

The process of reduction of Cr⁶⁺ ions (solution of potassium dichromate, K₂Cr₂O₇) in a water cathode was studied during a DC discharge in air. The concentration range of Cr⁶⁺ was (5.7–19) ×10^?5 mol/l and discharge current range was 20–80 mA. Cr⁶⁺ ions were shown to be reversibly reduced under a discharge action. The equilibrium degree of reduction increased with increasing initial concentration of the solution at fixed discharge current. At fixed initial concentration the reduction degree increased with increasing discharge current. The reduction degrees so obtained were 0.34–0.84. A kinetic scheme of the processes taking place in a solution was proposed. The calculated data obtained as a result of application of this scheme described well the experimental results on Cr⁶⁺ kinetics. The main processes of Cr⁶⁺ reduction and Cr³⁺ oxidation were revealed. HO ₂ ^· radicals and hydrogen peroxide were shown to be responsible for Cr⁶⁺ reduction whereas ^·OH radicals and O₂ molecules provide the reverse process of Cr³⁺ oxidation to Cr⁶⁺. The mechanism of action of phenol additives improving the process efficiency is discussed. The efficiency of phenol action as a radical scavenger was shown to be determined with its mass-transfer to the reaction area rather than chemical reaction rate.     

Catalytic Properties of TiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles in Plasma Chemical Treatment

We proposed here a new process coupling dielectric barrier discharge (DBD) plasma with magnetic photocatalytic material nanoparticles for improving yield in DBD degradation of methyl orange (MO). TiO₂ doped Fe₃O₄ (TiO₂/Fe₃O₄) was prepared by the sol-gel method and used as a new type of magnetic photocatalyst in DBD system. It was found that the introduction of TiO₂/Fe₃O₄ in DBD system could effectively make use of the energy generated in DBD process and improve hydroxyl radical contributed by the main surface Fenton reaction, photocatalytic reaction and catalytic decomposition of dissolved ozone. Most part of MO (88%) was degraded during 30 min at peak voltage of 13 kV and TiO₂/Fe₃O₄ load of 100 mg/L, with a rate constant of 0.0731 min^?1 and a degradation yield of 7.23 g/(kW h). The coupled system showed higher degradation efficiency for MO removal.     

Study of the thermal decomposition of MSO4 (M = Zn(II), Cd(II), Hg(II)) in a sodium nitrate—potassium nitrate melt

MSO₄ (M = Zn²⁺, Cd²⁺, Hg²⁺) dissolves in the molten NaNO₃—KNO₃ eutectic and is decomposed on further heating. The kinetics of decomposition have been studied at different temperatures. The decomposition of CdSO₄ and HgSO₄ in the eutectic melt obey first-order kinetics whereas the decomposition of ZnSO₄ at 420–460°C obeys second-order kinetics. However, at 480°C the decomposition of ZnSO₄ obeys first-order kinetics. The mechanism of decomposition has been given as M²⁺ +SO^2?₄ +Na⁺ +K⁺ +2NO^?₃ ? (Na,K)SO₄ + M²⁺ +2NO^?₃ M²⁺ +NO^?₃ → MO+NO⁺₂ NO^?₃ +NO⁺₂ → NO₂ + $\text{1}\text{2}$O₂ Some of the end products have been analysed by X-ray diffraction.     

Comparative Study of Influence of Experimental Configuration on Densities of Active Species in the Early Afterglows of N2/(0–2.5%)H2 HF Flowing Plasmas

Afterglows of mixed gas of N₂ and H₂(0–2.5%) flowing microwave discharges in a 5 mm diameter tube connected to a 5 L reactor via a tube of 1.8 cm diameter and 50 cm long, have been studied using optical emission spectroscopy. The obtained results at the entrance of the afterglow tube of 1.8 cm diameter: Short time afterglow (SA), (10^–3 s) and inside the 5 L reactor: Long time afterglow (LA), (10^–2 s) were then compared. It was found that, in N₂ at 2 Torr, 0.5 slpm, the active specie density ratios had a constant value of 10^–2 for N/N₂, but decreased respectively from 10^–3 to 10^–4 for N₂ (X,v?>?13)/N₂ and from 10^–6 to 10^–8 for N⁺₂ /N₂. By directly connecting the discharge tube inside the 5 L reactor, the density increases by 10 for N₂ (X,v?>?13) and by 10² for N₂⁺ by changing the afterglow from LA(10^?2 s) to a SA(10^–3 s). Moreover and by adding 1% of H₂ to N₂, the N/N₂ and H/H₂ ratios had constant values of 1% and 0.2% respectively. The SA(10^–3 s) appeared to be more efficient for surface treatments than the LA (10^–2 s).

     

Electrochemical method for sulphur dioxide removal from flue gases: Application on sulphuric acid plant in Tunisia

This article presents an electrochemical method for sulphur dioxide removal; the idea consists to couple the phenomenon of electrolysis upstream to the sulphuric acid plant. Otherwise, this proposition consists in modifying the hybrid cycle Westinghouse by the elimination of the sulphuric acid decomposition stage, which corresponds to 61% of the energy distribution of this cycle. The step of the decomposition is replaced by the exploitation of the quantity of sulphur dioxide emissions SO₂ stemming from the process of sulphuric acid H₂SO₄ production. The industrial complex of Gabès in South Tunisia is selected to be the case study complex. In fact, most industries are chemical oriented, the fast growing numbers of H₂SO₄ factories have resulted in fairly serious air pollution, especially sulphur dioxide SO₂ pollution. To confirm the efficiency of this process, a mass balance study was made on the sulphuric acid plant, which used a double contact/double absorption process; this study demonstrates that this new method can treat 8 t d^?1 of sulphur dioxide, recover 12 t d^?1 of sulphuric acid of title 50% and produce 6889 m³ d^?1 of the hydrogen. This idea can achieve economical and environmental benefits. It is concluded that the usage of this electrochemical process can significantly reduce the SO₂ air pollution in Gabès (South Tunisia) by the elimination of 46.94 t d^?1 of SO₂. The results obtained are ambitious for future application of the new process, which can succeed in the realisation of 3.92 million dollars of gain every day.     

Removal of Oil Products from Water Using a Combined Process of Sorption and Plasma Exposure to DBD

The paper presents the results of studies of a combined process involving the sorption of engine oil on a sorbent (diatomite) followed by regeneration of the sorbent by plasma-oxidative destruction of oil in DBD of atmospheric pressure in oxygen. The process parameters (gas flow rate, sorbent mass, power, treatment time), which provide the possibility of fivefold regeneration of the sorbent and 100% degree of oil decomposition, are revealed. It was found that the kinetics of oil degradation obeys the pseudo-first kinetic order equation with a rate constant of 0.017 s^?1. The energy efficiency of the decomposition was 0.169 molecules of oil per 100 eV of input energy. It is shown that treatment of the sorbent for 5 min leads to the complete decomposition of oil. The products of oil decomposition are carboxylic acids, aldehydes and CO₂. Complete removal of acids and aldehydes requires the time of about 40 min. The possible participation of ozone in the oxidative degradation of oil is discussed.     

Double-layer capacitance of waste coffee ground activated carbons in an organic electrolyte

Using ZnCl₂ activation we prepared a series of carbon electrodes from waste coffee grounds to study the effect of mesopores on double-layer capacitance in a tetraethyl ammonium tetrafluoroborate/acetonitrile electrolyte. The activated carbon with the largest mesopore volume achieved an energy density of 34 Wh kg^?1 at low current loads, and significantly retained an energy density of 16.5 Wh kg^?1 and specific capacitance of more than 100 F g^?1 at fast charge–discharge rates (20 A g^?1). The effect of mesopores on capacitance at fast charge–discharge rates is discussed.     

An acidic cellulose–chitin hybrid gel as novel electrolyte for an electric double layer capacitor

A novel acidic cellulose–chitin hybrid gel electrolyte including binary ionic liquids (ILs) with an aqueous H₂SO₄ solution was prepared for an electric double layer capacitor (EDLC). Its electrochemical characteristics were investigated by galvanostatic charge–discharge measurements. The test cell with a hybrid gel electrolyte shows a specific capacitance of 162 F g^?1 at room temperature, which is higher than that for a cell with an H₂SO₄ electrolyte, 155 F g^?1. This hybrid gel electrolyte exhibits excellent high-rate discharge capability in a wide range of current densities as well as an aqueous H₂SO₄ solution. The discharge capacitance of the test cell can retain over 80% of its initial value in 100,000 cycles even at a high current density of 5000 mA g^?1.     

Impedance study on the correlation between phase transition and electrochemical degradation of Si-based materials

In order to explain the relationship between physical change and electrochemical degradation of Co–Co₃O₄ coated Si, impedance spectroscopy on Co–Co₃O₄ coated Si was conducted at various states during charge or discharge. Nyquist plots during Li⁺ insertion (charge) showed a unique behavior that below 70 mV vs. Li/Li⁺, the more Li⁺’s were inserted into the electrode, the larger its comprehensive resistance was getting. During Li⁺ extraction (discharge), electrode resistance was decreased after going through 0.43 V vs Li/Li⁺. When these data were fitted with the ordinary equivalent circuit which is composed of electrolyte resistance, charge transfer resistance and contact resistance, there was an abrupt augmentation of charge transfer resistance below 70 mV vs. Li/Li⁺ during charge, whereas there was its drastic diminishment between 0.2 and 0.5 V vs. Li/Li⁺ during discharge. Because these potential regions are each related to amorphous Li_xSi-to-Li₁₅Si₄ transition and vice versa, it could be shown that the formation and decomposition of Li₁₅Si₄ is responsible for the electrochemical degradation of Co–Co₃O₄ coated Si.     

Fabrication and electrochemical properties of the Sn–Ni–P alloy rods array electrode for lithium-ion batteries

A new ternary Sn–Ni–P alloy rods array electrode for lithium-ion batteries is synthesized by electrodeposition with a Cu nanorods array structured foil as current collector. The Cu nanorods array foil is fabricated by heat treatment and electrochemical reduction of Cu(OH)₂ nanorods film, which is grown directly on Cu substrate through an oxidation method. The Sn–Ni–P alloy rods array electrode is mainly composed of pure Sn, Ni₃Sn₄ and Ni–P phases. The electrochemical experimental results illustrate that the Sn–Ni–P alloy rods array electrode has high reversible capacity and excellent coulombic efficiency, with an initial discharge capacity and charge capacity of 785.0 mAh g^?1 and 567.8 mAh g^?1, respectively. After the 100th discharge–charge cycling, capacity retention is 94.2% with a value of 534.8 mAh g^?1. The electrode also performs with an excellent rate capacity.     

Solid-state decomposition studies on fluoroperoxo species of transition metals. Part VI. Kinetics of isothermal decomposition of M2Zr2(O2)2F6 · 2 H2O (M = Rb+, or Cs+)

The decomposition of solid fluoroperoxozirconates of alkali metals, M₂Zr₂(O₂)₂F₆ · 2 H₂O (M = Rb⁺, Cs⁺), is carried out in vacuum under isothermal conditions. The stoichiometry of the reaction may be represented by the equation, M₂Zr₂(O₂)₂F₆ · 2 H₂O(S) — M₂Zr₂O₂F₆(s) + O₂(g) + 2 H₂ O(g) (condensed). The fractional decomposition α is determined by measuring the pressure of oxygen evolved during pyrolysis with a McLeod gauge. The α values range from 0.06 to 0.70 for the rubidium and from 0.06 to 0.79 for the caesium species in the temperature ranges 107–202°C and 101–219°C, respectively. The α—time data for both compounds show that the kinetics are deceleratory throughout the course of the decomposition reaction. In both compounds, the initial stages of decomposition are described by a unimolecular decay law, while the later stages obey a contracting volume equation at all temperatures. The activation energies from Arrhenius plots are 14.0 and 10.9 kcal mole^?1 for the rubidium and 12.9 and 11.2 kcal mole^?1 for the caesium compound.     

Electrodeposited PbO2 thin film on Ti electrode for application in hybrid supercapacitor

PbO₂ thin films were prepared by pulse current technique on Ti substrate from Pb(NO₃)₂ plating solution. The hybrid supercapacitor was designed with PbO₂ thin film as positive electrode and activated carbon (AC) as negative electrode in the 5.3 M H₂SO₄ solution. Its electrochemical properties were determined by cyclic voltammetry (CV), charge–discharge test and electrochemical impedance spectroscopy (EIS). The results revealed that the PbO₂/AC hybrid supercapacitor exhibited large specific capacitance, high-power and stable cycle performance. In the potential range of 0.8–1.8 V, the hybrid supercapacitor can deliver a specific capacitance of 71.5 F g^?1 at a discharge current density of 200 mA g^?1(4 mA cm^?2) when the mass ratio of AC to PbO₂ was three, and after 4500 deep cycles, the specific capacitance remains at 64.4 F g^?1, or 32.2 Wh Kg^?1 in specific energy, and the capacity only fades 10% from its initial value.     

Calorimetric measurements of sodium chloride dihydrate (hydrohalite)

Calorimetric measurements of sodium chloride dihydrate NaCl·2H₂O (mineral name hydrohalite) were carried out with using DSC. Heat capacity from 190 to 250 K was measured and found to increase from 109 to 137 J mol^?1 K^?1. The enthalpy of formation of hydrohalite from solid ice and halite at 273.15 K was derived from the thermal effect of melting/decomposition in DSC measurements and found to be close to ??1.8 kJ mol^?1. The same DSC results show clearly that the upper temperature limit for the existence of hydrohalite is several degrees greater than the current value of 273.15 K accepted for the peritectic decomposition of hydrohalite. The phase diagram of the NaCl–H₂O system needs correction.

     

Determination of chlorine species by capillary electrophoresis – mass spectrometry

The applicability of CZE with mass spectrometric detection for the determination of four chlorine species, namely chloride and three stable chlorine oxyanions, was studied. The main aspects of the proper selection of BGE and sheath liquid for the CE‐MS determinations of anions with high mobility were demonstrated, pointing out the importance of pH and the mobility of the anion in the BGE. The possibility of using uncoated fused silica capillary and common electrolytes for the separation was shown and the advantage of using extra pressure at the inlet capillary end was also presented. The linear range was found to be 1–100 µg/mL for ClO₃^? and ClO₄^?, 5–500 µg/mL for ClO₂^?, and 25–500 µg/mL for Cl^?, but the sensitivity can be greatly improved if larger sample volume is injected and electrostacking effect is utilized. The LOD for ClO₃^? in drinking water was 6 ng/mL, when very large sample volume was injected (10 000 mbar·s was applied).     

Photophysical and photochemical studies of thifensulfuron-methyl herbicide in aqueous solution

The photophysical and photochemical studies of a sulfonylurea herbicide, thifensulfuron-methyl (THM), have been investigated in a buffered aqueous solution. In the first part, the influence of pH on the spectroscopic properties was studied. This allowed the determination of the ground and excited state acidity constants, pK_a = 4 and 4.4, respectively, thus exhibiting the potential existence of a photoinduced protonation in the singlet state. In the second part, the photolysis kinetics was studied at different pH and varying oxygen concentrations, using an HPK 125 W lamp and followed up by the identification of photoproducts formed under continuous photo-irradiation. The kinetics results suggest that the photolysis process is faster in acidic (k = 3 × 10^?4 s^?1) than in basic medium (k = 9.8 × 10^?5 s^?1). The photolysis products were identified by high performance liquid chromatography HPLC-DAD, HPLC–MS and HPLC–MS–MS. In order to obtain a better understanding of the photodegradation mechanism, a laser flash photolysis study was performed. By comparing the quenching rate constant (k_q = 9.64 × 10⁸ mol^?1 l s^?1) obtained from triplet state quenching by molecular oxygen and from the Stern–Volmer relation (k_q = 0.41 × 10⁸ mol^?1 l s^?1), the role of the singlet state in the photodegradation process was demonstrated. The photoproducts originating from both singlet and triplet excited states have been identified and hypothetical photodegradation pathways of the thifensulfuron-methyl in aqueous solution are proposed.