Destruction of organic dyes in aqueous solution by low-temperature plasma jet treatment

A method for the destruction of organic compounds in their aqueous solutions using a plasma jet, generated by a pulse power source, at atmospheric pressure in air has been proposed. The acid–base dyes Phenol Red and Methyl Orange have been used as model compounds. The kinetics of degradation of these compounds and the formation kinetics of some products have been studied.     

Measurement and energy correction due to charge carrier lifetimes in large HPGe spectrometers

This work addresses the energy spectrum correction due to increased charge carrier collection times in larger HPGe spectrometers. The energy of the radiation interaction is expected to be proportional to the total collected charge. This is increasingly not true with larger HPGe spectrometers. Some charge is lost as the total charge travels from the interaction location to the collection electrode. This path dependent loss of charge results in decreased energy resolution. In HPGe spectrometers, this process is characterized by the charge carrier lifetime constant and is given as an exponential function of the charge carrier collection time divided by this constant. Thus large detectors can experience exponential decrease in energy resolution as charge carrier collection time increases. We studied the effect of charge carrier lifetime on energy resolution for a p-type point contact HPGe spectrometers using pulse shape analysis. We present a method using the rise time to correct for the charge carrier lifetime on a pulse by pulse basis for a given HPGe spectrometer.     

Excited states of the high-frequency vibrational modes and kinetics of ultrafast photoinduced electron transfer

The effect of the carrier frequency of the exciting laser pulse on the kinetics of intramolecular photoinduced charge transfer in the multi-channel stochastic model is studied. It is shown that the population of different states of high-frequency intramolecular modes upon varying the frequency of the excitation pulse can considerably alter the rate constant of ultrafast charge transfer. It is found that a negative vibrational spectral effect is expected in the vicinity of a barrier-free area (the rate constant of photoinduced charge transfer decreases along with the carrier frequency of the excitation pulse), while a positive effect is predicted in areas of high and low exergonicity (an inverse dependence). It is concluded that the value of the spectral effect falls along with the time of vibrational relaxation. For ultrafast photo-induced charge transfer, however, it remains considerable up to relaxation times of 100 fs.     

W–C Electrode Erosion in a Pulsed Arc Submerged in Liquid

Electrode erosion was studied in pulsed arcs ignited between two electrodes comprised of 99.99% C (graphite) and 99.5% W submerged in deionized water or analytical (99.8%) ethanol. In the both cases the erosion rate increased proportionally to the pulse energy, and the total electrode erosion per unit energy was inversely proportional to the discharge pulse duration. Fifteen and sixty-μF discharge capacitors were used for formation of the pulses in water. It was obtained that, respectively (a) erosion of the tungsten anode (W_a) was by factors of 5–6 and ∼10 greater than that of the carbon (C_c) cathode; (b) erosion of the carbon anode (C_a) was by a factor of 1.34 greater and by a factor of 2.65 less than that of the tungsten cathode (W_c); (c) the total erosion rate of both electrodes (anode and cathode) per unit pulse energy for the W_a–C_c pair was greater by factors of 11 and 12.5 than that for the W_c–C_a pair.     

Time-resolved spectroscopy at the picosecond laser-triggered electron accelerator ELYSE

ELYSE is a fast kinetics center created for pulse radiolysis with picosecond time-resolution. The facility is a 4–9 MeV electron accelerator using a subpicosecond laser pulse to produce an electron pulse from a Cs₂Te semiconductor photocathode and RF gun technology for the electron acceleration. The pulse duration is around 5 ps at low charge (<2 nC) and high energy (9 MeV), and is under routine conditions 10 ps at higher charge (5 nC) and >8 MeV. The dark current at the target is less than 1% of the pulse photocurrent.Time-resolved absorbance measurements in cells placed in front of the electron beam are achieved using pulsed laser diodes, or a xenon flash lamp as light sources, and photodiodes connected to a 3 GHz transient digitizer or a streak camera (250–800 nm range and 3.7 ps time resolution) as detection instruments. In addition, the synchronization between the laser beam and the electron beam is exploited to measure the absorbance by a pump-probe set-up, the pump being the electron pulse produced by the laser pulse, and the probe being part of the laser beam (120 fs–3 ps) delayed by a variable optical line.     

脉冲光电子枪中光电子束性能研究

利用新设计的脉冲光电子枪,研究了光电子束的能量分布,光电子数密度与激光强度的关系和光电子在电离区内的滞留时间。大部分电子的能量为光发射电子的剩余能量,但是由于电子的空间电荷效应,电子能量分布具有加宽现象·每个激光脉冲发射到电离区内的光电子数密度在109/cm3以上。     

Computer simulation of the kinetics of radiation-induced delayed fluorescence in nonpolar solutions

The processes of the formation of excited states on the nanosecond timescale in irradiated alkane solutions of positive charge and energy acceptors were studied by means of computer simulation in the single-spur approximation as an the example. The model involved pairwise contact interactions between all transient species produced in the same spur with allowance for their spin state. The effects of external magnetic and electric fields on the kinetics of delayed fluorescence were calculated, depending on the spur size and the initial number of ion pairs in the spur. It was shown that energy transfer from excited solvent molecules to an acceptor and the annihilation of luminophore triplet molecules should be taken into consideration in the simulation of the kinetics of delayed fluorescence of irradiated solution even at a low average ionization density.     

Fluorescent probes for monitoring the pulsed‐laser‐induced photocuring of poly(urethane acrylate)‐based adhesives

Fluorescence spectroscopy was used to study the kinetics of polymerization of acrylic adhesive formulations exposed to a 355‐nm pulsed emission from an Nd‐YAG laser. Nine fluorescent probes were used for monitoring the laser curing, showing different sensitivities. In general, the fluorescence intensity emission increased as crosslinking occurred. In addition, solvatochromic fluorescent probes showed a blueshift in their emission. A relative method was applied for the evaluation of the polymerization rates in three different acrylic systems. Special features of pulsed‐laser‐induced polymerization were treated in detail, such as the influence of the laser pulse frequency and the incident laser beam intensity. The polymerization rate slowed down as the pulse repetition rate decreased. An inhibition period due to oxygen quenching was observed, and it was highly dependent on the laser repetition rate and the nature of the photoinitiator. The effect of the laser beam intensity on the kinetics of such fast reactions was studied. In general, increasing the laser energy improved the rate of polymerization. The degree of cure improved as the polymerization rate increased as a result of faster crosslinking, rather than relaxation volume kinetics. Moreover, a saturation rate effect occurred that depended on the photoinitiator. The different behaviors of the two photoinitiators in the curing of the same acrylic formulation was explained on the basis of primary radical termination. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1227–1238, 2004     

Performance of compact pulse radiolysis system using a photocathode RF gun

A compact pulse radiolysis system using a photocathode RF gun was installed at Sumitomo Heavy Industries. Some performance tests were conducted concerning the electron beam and the laser pulse. The energy and the per-pulse charge of the electron beam were measured to be 1.75 MeV max. and 1 nC. The fluctuation of the charge was restricted within 2%. The pulse widths of the electron pulse and the analyzing laser pulse were 20 ps and 15 ps, respectively. The timing jitter between electron pulse and the laser pulse was ±5.7 ps. Based on these measurements, the all-over time resolution can deduced to be about 25 ps.     

A High‐Energy Charge‐Separated State of 1.70 eV from a High‐Potential Donor–Acceptor Dyad: A Catalyst for Energy‐Demanding Photochemical Reactions

A high potential donor–acceptor dyad composed of zinc porphyrin bearing three meso‐pentafluorophenyl substituents covalently linked to C₆₀, as a novel dyad capable of generating charge‐separated states of high energy (potential) has been developed. The calculated energy of the charge‐separated state was found to be 1.70 eV, the highest reported for a covalently linked porphyrin–fullerene dyad. Intramolecular photoinduced electron transfer leading to charge‐separated states of appreciable lifetimes in polar and nonpolar solvents has been established from studies involving femto‐ to nanosecond transient absorption techniques. The high energy stored in the form of charge‐separated states along with its persistence of about 50–60 ns makes this dyad a potential electron‐transporting catalyst to carry out energy‐demanding photochemical reactions. This type of high‐energy harvesting dyad is expected to open new research in the areas of artificial photosynthesis especially producing energy (potential) demanding light‐to‐fuel products.     

Spectrophotometric studies of the formation of charge transfer complex of iron(III) with N,N′-bis(2-pyridylmethylidene)-1,2-diiminoethane di-Schiff base ligand in methanol

The complex formation reaction between N,N′-bis(2-pyridylmethylidene)-1,2-diiminoethane (BPIE) di-Schiff base ligand as an electron donor and iron(III) chloride as an electron acceptor have been studied spectrophometrically in methanol at 28°C. The values of equilibrium constants, K and molar absorptivities, ε were obtained from the Benesi–Hildebrand, Scott and Foster–Hammick–Wardley equations. The results indicate the formation of 1?:?1 charge transfer complex. The absorption band energy of the complex, E _CT, the ionization potential of the BPIE Schiff base ligand, I ^D, and the Gibbs energy changes of the above reaction, ΔG ⁰, were calculated. Finally, the kinetics of the complex formation reaction were studied and was found to be second-order in each reactant. The values of the rate constants of the forward and reverse reactions k ₁ and k _?1 were determined.     

A Z‐Scheme Strategy that Utilizes ZnIn2S4 and Hierarchical VS2 Microflowers with Improved Charge‐Carrier Dynamics for Superior Photoelectrochemical Water Oxidation

One of the major limiting factors for efficient photoelectrochemical water oxidation is the fast recombination kinetics of photogenerated charge carriers. Herein, we propose a model system that utilizes ZnIn₂S₄ and hierarchical VS₂ microflowers for efficient charge separation through a Z‐scheme pathway, without the need for an electron mediator. An impressive 18‐fold increase in photocurrent was observed for ZnIn₂S₄–VS₂ compared to ZnIn₂S₄ alone. The charge‐transfer dynamics in the composite were found to follow a Z‐scheme pathway, which resulted in decreased charge recombination and greater accumulation of the surface charge. Furthermore, slow kinetics of the surface reaction in the ZnIn₂S₄–VS₂ composite correlated to an increased surface‐charge capacitance. This feature of the composite material facilitated partial storage of the photogenerated charge carriers (e^?/h⁺) under illumination and dark‐current conditions, thus storing and utilizing solar energy more efficiently.     

Kinetics of bulk polymerization of trimeric phosphonitrilic chloride

The kinetics of the pure bulk polymerization of trimeric phosphonitrilic chloride were investigated in the temperature range 240–255°C. The reaction was found to be secondorder with an activation energy of 57 kcal./mole. Polymerization catalyzed by benzoic acid was first-order, and the reactivities of benzoic acid and sodium benzoate at 235°C. were found to be about similar. The volatile decomposition products for the benzoic acid reaction were identified. Mechanisms are postulated for the catalyzed and uncatalyzed reactions.     

Kinetic analysis of photoelectrochemical hydrogen evolution over p-type silicon in acidic aqueous solutions of electrolytes

The kinetics of photoelectrochemical hydrogen evolution at p-Si single crystals in acidic aqueous solutions of electrolytes under pulse photoexcitation was studied. Despite a low stability of the silicon surface under the experimental conditions, a distinct interrelation between the characteristic time of interfacial charge transfer and stationary current was found. The determination of the characteristic transfer time does not need the detailed elaboration of generation-recombination processes in the semiconductor. The steady-state current density was shown to be determined both for the dark current and photocurrent by the surface charge density. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1724–1728, October, 2000.     

Microwave‐synthesized Pepper Peduncle Carbon,Characterization, and Its Adsorption Studies

Adsorption on activated carbon is an efficient method for the removal of toxic dyes. However, since commercially available charcoal is quite expensive, activated carbon obtained from agricultural by‐products may serve as a good replacement. In this study, activated carbon was prepared from pepper peduncle, an agricultural waste product, by microwave activation. The synthesized carbon was characterized by X‐ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and thermal gravimetric analysis techniques. It was then used for the adsorption of methylene blue dye from an aqueous solution, which was studied as a function of the dye concentration, contact time, and temperature. The adsorption data were fitted to Freundlich and Langmuir isotherm models. The adsorption kinetics was studied by employing first‐ and second‐order kinetic models, and it was found that the adsorption of methylene blue on the synthesized activated carbon follows a second‐order kinetic model. Effect of temperature on the adsorption process was studied, and the thermodynamic parameters such as activation energy, change in enthalpy, entropy, and free energy of adsorption were calculated on the basis of the absolute theory of reaction rate expressions. About 99.5–91.8% of the dye was removed for an initial dye concentration in the range 20–100 mg/g in 1 h. Thus the synthesized activated carbon was found to be very efficient in adsorbing the dye.     

Thermal decomposition of methyl β‐hydroxyesters in m‐xylene solution

The products and kinetics of the thermal decomposition of several methyl‐β‐hydroxyesters in m‐xylene solution have been studied. It has been shown that all β‐hydroxyesters studied pyrolyze to form a mixture of methyl acetate and the corresponding aldehyde or ketone and that the decomposition follows first‐order kinetics and appears to be homogeneous and unimolecular. The rate pyrolysis of methyl‐3‐hydroxypropanoate, methyl‐3‐hydroxybutanoate, and methyl‐3‐hydroxy‐3‐methylbutanoate has been measured between 250 and 320°C. The relative rates of primary, secondary, and tertiary alcohols at 553 K are 1.0, 8.5 and 54.1, respectively. The absence of large substituent effects indicates that little charge separation occurs during the breaking of carbon–carbon single bond. The activation entropy is compatible with a semipolar six‐membered cyclic transition state postulated for other β‐hydroxy compounds. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 92–96, 2007     

Kinetics of nonisothermal crystallization of Cs2O–Fe2O3–P2O5 glasses

The crystallization kinetics of Cs₂O–Fe₂O₃–P₂O₅ glasses containing 12.5–27 mol% Cs₂O were studied by using differential scanning calorimetry under nonisothermal conditions. Strong dependence of activation energy with temperature was observed, indicating the complex nature of the crystallization process. The various crystallization products were identified by X-ray diffraction technique. CsFeP₂O₇ was found to be the major crystalline phase in all cases. The overall activation energy obtained by classical model-free kinetic method was compared with that of isoconversional method; and from the results, the dependence of activation energy on extent of reaction and average temperature was delineated.     

Kinetics of copper slag oxidation under nonisothermal conditions

The kinetics of air copper slag oxidation under nonisothermal conditions is studied using simultaneous TG–DTA at a varying heating rate of slag and flow rate of the oxidizing gas flux. The values of the kinetic parameters, activation energy and pre-exponential factor, have been determined based on: data from DTA by the methods of Kissinger and Ozawa; data from TG using an isoconversion method and the computation procedures of Ozawa–Flynn–Wall and Kissinger–Akahira–Sunose. No relationship between the kinetic parameters and the oxidation gas flow rate has been established. The changes of the phase composition with temperature are investigated by X-ray powder diffraction analysis on the basis of data obtained for the products formed at the different stages of the oxidation process. The morphology of the oxidized slag as well as the elements distribution is studied by electron microscopy and EDS analysis.     

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.     

Recent Developments on Understanding Charge Transfer in Molecular Electron Donor-Acceptor Systems

Charge transfer (CT) in molecular electron donor-acceptor systems is pivotal for artificial photosynthesis, photocatalysis, photovoltaics and fundamental photochemistry. We summarized the recent development in study of CT and discussed its application in thermally activated delayed fluorescence (TADF) emitters. The direct experimental proof of the spin multiplicity of the charge separated (CS) state with pulsed laser excited time-resolved electron paramagnetic resonance (TREPR) spectroscopy was discussed. Experimental determination of the electron exchange energy (J) of the CS state, with magnetic field effect on its yield or lifetime was introduced. The electron spin transfer accompanying the CT, studied with pulsed EPR spectra was briefly discussed. Tuning of the CT yield and kinetics with selective vibration excitation of the linker (the bridge) with IR pulse was presented. Above all, these studies show that there are more fun than simply monitoring the formation of the cations and anions and the kinetics or CS yields in this area.