Electron beam induced decomposition of chlorinated aromatic compounds in waste incinerator offgas

Gaseous emissions of polychlorinated dibenzo-dioxins and -furanes (PCDD/F) in incinerator flue gas are decomposed to below 0,1 ng m_N⁻³ by the irradiation with accelerated electrons. A mobile off gas cleaning plant (AGATE-M), equipped with a 200 keV electron accelerator (EB), was used to treat a flow of 1000 m_N³ h⁻¹ of flue gas from a waste incinerator. Very high decomposition efficiencies were obtained at a dose of 5 – 10 kGy. A computer model (AGATE-code) was developed to analyze the gas phase chemistry of the process. The experimental and the theoretical results are reported and compared.     

Direct hetero-excimer formation from radical ions

Chemiluminescent reactions in ether solutions between radical anions (A⁻) and tri-p-tolylaminium perchlorate (D⁺ClO₄⁻) are investigated. The results are interpreted on the basis of the reaction sequence: where ¹(D⁻D⁺) is the hetero-excimer.     

Oxidation of crystal violet and malachite green in aqueous solutions — a kinetic spectrophotometric study

The reactions of two triphenyl methane (TPM) dyes—crystal violet (CV⁺) and malachite green (MG⁺)—with N₃^• and OH^• radicals were studied by pulse radiolytic kinetic spectrophotometry. The rate constants for the reaction of the cationic dyes (D⁺) with N₃^• are (9.0±0.6)×10⁹ and (3.0±0.2)×10⁹ dm³ mol⁻¹ s⁻¹ respectively and those for the reaction with OH^• are obtained as (8.0±0.6)×10⁹ and (1.1±0.1)×10⁹ dm³ mol⁻¹ s⁻¹ respectively. The transient spectra resulting from the oxidation of the dyes were characterized. The time-resolved spectra indicate that the reaction with OH^• radicals initially generates an adduct which subsequently dissociates to form the radical dication D^•2+. The D^•2+ species decay by further reaction with the parent dye.     

High power electron accelerators for flue gas treatment

Over 1000 accelerators based on different principles have been constructed and used in the field of radiation chemistry and radiation processing. One of the radiation processes which was successfully demonstrated in many laboratories and pilot plant facilities is the reduction of SO₂ and NO_x pollutants from flue gases emitted during fuel combustion in boilers for electrical power and heat production. The full scale industrial implementation of an electron beam process for flue gases treatment would require accelerator modules with a beam power of over 500 kW and electron energy in the range 1–1.5 MeV. The 500 MW power plant may require 5–8 MW of electron beam power deposited in the flue gas.     

Technological applications of BINP industrial electron accelerators with focused beam extracted into atmosphere

Simultaneously with production of industrial accelerators BINP develops new EB technologies. For this purpose the set of equipment based on electron accelerators was installed. The accelerator has an energy range of 0.8–1.5 MeV and a maximum electron beam power of 100 kW. Electron beam is extracted into the atmosphere through the system of diaphragms with output holes about 1 mm in diameter. The operational vacuum in the accelerating tube is provided by a differential pumping system. The extraction device is equipped with additional scanning magnets. It allows the operator to change average beam power density in extra wide region from 10 to 10⁷ Wt/cm². The focused beam has many applications due to its unique properties.     

Application of the 30 MeV microtron for gamma and neutron activation analysis

Based on studies of variable multiplicity electron acceleration, the power-current microtron, a cyclic electron accelerator up to energies of 30–35 MeV has been developed at the Institute on Physical Problems of the Academy of Sciences of the USSR. The 1–1.5 kW electron beam of the microtron is comparable to the power output of modern linear accelerators operating at similar energies. At the same time, the microtron has a number of significant advantages, due to the simplicity of design of both accelerator and ultrahigh-frequency tract, the high efficiency of ultrahigh-frequency power utilization, good operating characteristics, strictly monochromatic electron beams (variations not exceeding ±50 keV at 30 MeV) and the possibility of continuously changing particle energy as required by the given experimental task.     

Energetic distribution of the electrons from a 200 keV beam in polyurethane layers : EGS4 calculation and FTIR analysis

The aim of this study is to characterize the chemical transformation of a polymer resulting from irradiation by a 200 keV electron beam. Thermoplastic PU polyetherurethane material was used and irradiation was performed with applied electron fluences in the range of 10¹⁴–10¹⁷ electron cm⁻² at 77 K.

The chemical changes have been observed by FTIR analysis of irradiated layers. A NH bond evolution study has allowed us to follow polymer degradation versus depth and fluence. The results have been compared to a simulation of electronic energy loss and to the energy spectrum of the generated electrons in the polymer using EGS4 code.     

Fluence measurements applied to 5–20 MeV/amu ion beam dosimetry by simultaneous use of a total-absorption calorimeter and a Faraday cup

A Faraday cup was fabricated for measuring the beam current of a few tens MeV/amu ion beams of the TIARA AVF cyclotron. It has been applied as a beam monitor for studying the characteristics of film dosimeters that are well-established for high doses of ⁶⁰Co γ-rays and 1 to 10 MeV electrons. A total absorption calorimeter designed to measure energy fluence has also been tested for estimating the uncertainty in fluence measurement of 5–20 MeV/amu ion beams, by simultaneous use of the calorimeter and the Faraday cup in a broad uniform fluence field. The estimated fluence was evaluated on the basis of nominal particle energy values derived from the cyclotron acceleration parameters. The average ratio of the measured fluence values to the estimated values is 1.024, and the average precision is within ±2% at a 68% confidence level, for most of the ion beams with a range of kinetic energy per nucleon, 5–20 MeV/amu, at an integrated charge above 5 nC/cm².     

Positron mobilities in isooctane, n-hexane and hexafluorobenzene

Positron mobilities in three nonpolar liquids, isooctane (2, 2, 4-trimethylpentane), n-hexane and hexafluorobenzene, were measured by observing the drift velocity of free positrons in the presence of an external electric field. The Doppler shift of the 511 keV annihilation line was measured as a function of the electric field up to 26 kV cm⁻¹ at room temperature. The free positron mobilities in isooctane and n-hexane were determined to be 69 ± 3 cm² V⁻¹ s⁻¹ and 53 ± 3 cm² V⁻¹ s⁻¹, respectively, whereas a much smaller value of 0 ± 7 cm² V⁻¹ s⁻¹ was obtained for hexafluorobenzene.     

Radiation degradation of polychlorinated biphenyls

Gradual dechlorination of the polychlorinated biphenyls (PCBs) in alkaline solutions in 2-propanol under the effect of high energy electrons (4.5 MeV) produced by electron accelerator has been studied using a flow-through apparatus of the volume of about 50 L. The dependence of both relative radiation chemical yield and the dechlorination degree on the initial concentration of OH⁻ ions or PCBs, absorbed dose as well as on dose rate has been investigated.     

Water diffusion in polyethylene modified by ion irradiation

Water diffusion in polyethylene (PE) modified by irradiation with 40keV Ar⁺ ions to fluences of 1 × l0¹² to 1 × l0¹⁵cm⁻² was studied. The diffusion experiments were performed in a temperature interval from 25 to 100 °C and for diffusion times of up to 3 h. The water incorporated was detected by infra-red spectroscopy, microgravimetry and by measuring contact angles. Maximum water uptake observed for the ion fluence of 1 × 10¹³cm⁻² may be connected with an increase in free volume fraction and oxidative processes in the PE surface layer modified by ion irradiation. For higher ion fluences, the available free volume is reduced owing to carbonization and crosslinking of the polymer and, accordingly, the water content decreases. The water incorporated in PE is mostly in the form of isolated molecules. At elevated temperature rediffusion of water is observed.     

Voltammetric determination of glucose based on reduction of copper(II)–glucose complex at lanthanum hydroxide nanowire modified carbon paste electrodes

A novel voltammetric method for the determination of β-d-glucose (GO) is proposed based on the reduction of Cu(II) ion in Cu(II)(NH₃)₄²⁺–GO complex at lanthanum(III) hydroxide nanowires (LNWs) modified carbon paste electrode (LNWs/CPE). In 0.1 mol L⁻¹ NH₃·H₂O–NH₄Cl (pH 9.8) buffer containing 5.0 × 10⁻⁵ mol L⁻¹ Cu(II) ion, the sensitive reduction peak of Cu(II)(NH₃)₄²⁺–GO complex was observed at −0.17 V (versus, SCE), which was mainly ascribed to both the increase of efficient electrode surface and the selective coordination of La(III) in LNW to GO. The increment of peak current obtained by deducting the reduction peak current of the Cu(II) ion from that of the Cu(II)(NH₃)₄²⁺–GO complex was rectilinear with GO concentration in the range of 8.0 × 10⁻⁷ to 2.0 × 10⁻⁵ mol L⁻¹, with a detection limit of 3.5 × 10⁻⁷ mol L⁻¹. A 500-fold of sucrose and amylam, 100-fold of ascorbic acid, 120-fold of uric acid as well as gluconic acid did not interfere with 1.0 × 10⁻⁵ mol L⁻¹ GO determination.     

Modeling the separation performance of nanofiltration membranes for the mixed salts solution

A new model is proposed to evaluate the separation performance of nanofiltration (NF) membranes for the mixed salts solution. In the model, the observed transmission of an ion through a NF membrane is applied to express the separation performance of the membrane for the ion in the mixed salts solution, which has a relationship with the total concentration, the equivalent fraction and the species of each ion in the mixed salts solution. The verification of the model was carried out in the permeation experiments of some mixed salts solutions ((1) Na⁺, Cl⁻ and F⁻; (2) Na⁺, K⁺ and Cl⁻; (3) Na⁺, F⁻, Cl⁻ and NO₃⁻; (4) Na⁺, Cl⁻, NO₃⁻ and SO₄²⁻) through three commercial NF membranes (ESNA 1-LF, ESNA 1 and LES 90). According to the permeation experiments of three NF membranes for some binary salts solutions, the competition coefficients of ions were obtained. The model evaluation results agreed quite well with the experimental data. Finally, the model was applied to evaluate the observed transmission of each ion in the mixed salts solution (Na⁺, F⁻, Cl⁻, NO₃⁻ and SO₄²⁻) through three NF membranes. The agreement between the model evaluation results and the experimental data indicated that the model is suitable for evaluating the separation performance of three NF membranes for the mixed salts solution.     

A new fluorescent probe of rhodamine B derivative for the detection of copper ion

A new fluorescent probe, rhodamine B hydrazide oxalamide (RBHO), which shows very weak fluorescence, was synthesized, and its fluorescence could be substantially enhanced by the addition of copper ion. The probe shows a high selectivity and sensitivity to copper ion by forming a 1:1 complex in acetonitrile, and the chelating is reversible. Limit of detection for copper ion in acetonitrile was found to be 3.7 × 10⁻⁸ mol L⁻¹. It was also found that copper ion could catalyze the hydrolysis of the probe in 50% (v/v) buffered (10 mM Tris–HCl, pH 7.0) water/acetonitrile giving a highly fluorescent product, and the fluorescence detection of copper ion was developed in this neutral buffered media with a detection limit of 6.4 × 10⁻⁷ mol L⁻¹. Determination of copper ion in water and synthetic samples in the presence of different interfering metal ions was successfully carried out with the new probe RBHO.     

Flow injection determination of iodide ion in a photographic developing solution using iodide ion-selective electrode detector

A potentiometric flow injection determination method for iodide ion in a photographic developing solution was proposed by utilizing a flow-through type iodide ion-selective electrode detector. The sensing membrane of the electrode was Ag₂S–AgI membrane. The response of the electrode detector as a peak-shape signal was obtained for injected iodide ion in a photographic developing solution. A linear relationship in the subnernstian zone was found to exist between peak height and the concentration of the iodide ion in a photographic developing solution in a concentration range from 0 to 6.0×10⁻⁵ mol l⁻¹. The relative standard deviation for ten injections of 2×10⁻⁵ mol l⁻¹ iodide ion in a photographic developing solution was 0.96% and the sampling rate was approximately 12–13 samples h⁻¹. The iodide ion could be determined under coexisting of an organic reducing reagent and inorganic electrolytes of high concentration in a photographic developing solution sample solution by the present method.     

Global minima of (C60)nCa, (C60)nF and (C60)nI clusters

Likely candidates for the lowest potential energy minima of (C₆₀)_nCa²⁺, (C₆₀)_nF⁻ and (C₆₀)_nI⁻ clusters are located using basin-hopping global optimisation. In each case, the potential energy surface is constructed using the Girifalco form for the C₆₀ intermolecular interaction, an averaged Lennard–Jones C₆₀–ion interaction, and a polarisation potential, which depends on the first few non-vanishing C₆₀ multipole polarisabilities. We find that the ions generally occupy the interstitial sites of a (C₆₀)_n cluster, the coordination shell being tetrahedral for Ca²⁺ and F⁻. The I⁻ ion has an octahedral coordination shell in the global minimum for (C₆₀)₆I⁻, however for 12  n  8 the preferred coordination geometry is trigonal prismatic.     

Formation of SF5 in electron attachment to SF6; swarm and beam results reconciled

Based on the results of recent swarm experiments, it has been proposed that the increase in the cross section for SF₅⁻ formation observed at an electron energy, E_e of about 0.3 eV in electron beam studies of electron attachment to SF₆ is due to the combined (opposing) effects of the vibrational heating of the molecule by the attached electron, which enhances the dissociation of the nascent (SF₆⁻)^* ion, and the reduction of the cross section for capture (s-wave) of the electron by SF₆ with increasing E_e. Further, it has been shown that the dissociation reaction is endothermic by 0.12 eV, and that, contrary to previous suggestions, there is no potential barrier to this dissociation reaction. Now we have carried out electron beam studies of the SF₆ attachment reaction in Berlin at gas temperatures, T_g, over the range 300 to 920 K and in Innsbruck at T_g below 300 K. These studies have provided support for the above proposals concerning the appearance of the SF₅⁻ peak and for a reaction endothermicity of 0.12 eV. Thus these studies have clarified the doubts about the products of the SF₆ attachment reaction at low electron energy.     

Carbon ion irradiation induced surface modification of polypropylene

Polypropylene was irradiated with ¹²C ions of 3.6 and 5.4 MeV energies in the fluence range of 5×10¹³–5×10¹⁴ ions/cm² using 3 MV tandem accelerator. Ion penetration was limited to a few microns and surface modifications were investigated by scanning electron microscopy. At the lowest ion fluence only blister formation of various sizes (1–6 μm) were observed, but at higher fluence (1×10¹⁴ ions/cm²) a three-dimensional network structure was found to form. A gradual degradation in the network structure was observed with further increase in the ion fluence. The dose dependence of the changes on surface morphology of polypropylene is discussed.     

Semiempirical and ab initio calculations on the alkaline hydrolysis of the β-lactam ring Influence of the solvent

We used semiempirical and ab initio calculations to investigate the nucleophilic attack of the hydroxyl ion on the β-lactam carbonyl group. Both allowed us to detect reaction intermediates pertaining to proton-transfer reactions. We also used ab initio calculations and the PM3 semiempirical method to investigate the influence of the solvent on the process. The AMSOL method predicts the occurrence of a potential energy barrier of 20.7 kcal mol⁻¹ due to the desolvation of the hydroxyl ion in approaching the β-lactam carbonyl group. Using the supermolecular approach and a water solvation sphere of 20 molecules around the solute, the potential energy barrier is lowered to 17.5 kcal mol⁻¹. Ab initio calculations using the SCRF method predict a potential energy barrier of 13.6 kcal mol⁻¹. These three values, especially the last two, are very close to the experimental value of 16.7 kcal mol⁻¹.     

Ab initio calculations of minimum-energy pathways of the nucleophilic addition of the H anion, LiH molecule and Li/H ion pair to acetylene and methylacetylene

Ab initio calculations were performed for special points of the minimal energy pathways (MEP) of the nucleophilic addition reactions of the isolated H⁻ anion, LiH molecule and Li⁺/H⁻ ion pair to acetylene (A) and methylacetylene (MA) molecules, proceeding in accordance (M) and against (aM) the Markovnikov's rule. All structural parameters were optimized using the restricted Hartree–Fock (RHF) method. For the addition of H⁻, the 6-31++G^* basis set was used and for the reactions of LiH and Li⁺/H⁻ the 6-31G^* basis set with the subsequent recalculation of single point energies, taking into account of electron correlation energy by means of the second-order Möller–Plesset perturbation theory at the MP2/6-31++G^** level. The results of calculations demonstrate, that the energy characteristics of both M- and aM-additions with H⁻ do not differ sufficiently (0.1–1.2 kcal/mol for the activation energies (ΔE_a) and the reaction heats (ΔQ)). The substitution of the H atom by the CH₃ group in A molecule results in practically the same values of ΔQ and ΔE_a. On the contrary, for the LiH molecule and Li⁺/H⁻ ionic pair, the M-addition is favorable (charge control). It is found that the presence of electrophile decreases the activation energy by 3–5 kcal/mol as compared with the addition of the isolated hydride ion H⁻.