The radiolysis of bromophenol blue in aqueous solutions

The effect of gamma radiation on the color intensity of aerated and oxygenated aqueous solution of bromophenol blue (BPB) was investigated. Ionizing radiation at increasing absorbed doses (D) brought about gradual bleaching (i.e. decrease in optical absorbance, -ΔA) of bromophenol blue solutions. The molar extinction coefficients of acidic, neutral, and alkaline solutions were measured and found to be independent of temperature during spectrophotometry between 20 and 40°C. Aerated and oxygen-saturated acidic solutions showed a linear response -ΔA vs D) up to doses of 2.4 and 2.1 kGy, respectively. Aerated alkaline solutions on the other hand showed a linear response up to 4.8 kGy. The decoloration yields for 5 × 10^-5 M bromophenol blue aqueous solutions, G(-BPB), obtained from the decrease in absorbance at 591 nm wavelength for acidic, neutral, and alkaline solutions, were 0.244, 0.113, and 0.098 (100 eV)^-1, respectively. The first-order rate constant for the reaction of OH radical with bromophenol, obtained from competition reactions with ethanol at pH 4, was found to be 9.1 +- 1.2 × 10⁹ M^-1 s^-1. The degree of decoloration of bromophenol blue in acidic solutions was found to decrease upon the addition of ethanol, G(-BPB) decreasing from 0.24 to 0.088 upon the addition of ethanol at a concentration of 10^-2M. Suggestions are made for possible radiation dosimetry in the dose range (0.1–5 kGy) by means of spectrophotometric analysis of absorption spectra.     

Final product analysis in the e-beam and gamma radiolysis of aqueous solutions of metoprolol tartrate

The radiostability of metoprolol tartrate aqueous solutions and the influence of the absorbed dose (0–50 kGy), dose rate (e-beam (EB) vs. gamma (γ)) and radioprotectors (pharmaceutical excipients) are investigated by HPLC-UV analyses and through computer simulations. The use of radioprotecting excipients is more promising than an increase in the dose rate to lower the degradation of metoprolol tartrate aqueous solutions for applications such as radiosterilization. The decontamination of metoprolol tartrate from waste waters by EB processing appears highly feasible.     

Low-temperature radiolysis of aqueous solutions of alkali

Russian Chemical Bulletin -     

The pulse radiolysis of aqueous solutions of simple RCN compounds

Fast kinetic spectrophotometry was used to study the absorption spectra of short-living intermediates produced by reactions of RCN molecules with H, e_aq⁻ and OH. The spectra were obtained on the microsecond time scale after an electron pulse from a Febetron 707 accelerator in aqueous solutions of the following compounds: hydrocyanic acid, acetonitrile, propionitrile, malononitrile and succinonitrile. It has been found that all intermediates absorb in the U.V. range (λ⩽300 nm) and disappear by fast bimolecular processes with decay rate constants of about 10⁹dm³mol⁻¹s⁻¹. In the presence of an efficient scavenger for hydroxyl radicals, the same transient spectra were registered in acid and neutral solutions suggesting that the protonations of e_aq⁻ adducts of these RCN molecules were complete within a submicrosecond time interval.     

Pulse radiolysis of aqueous solutions of tetraphenylphosphonium ions

The reactions of tetraphenylphosphonium ion (Ar₄P⁺) with e_aq⁻, H atoms and OH radicals have been investigated. The absorption spectra of three transient species were obtained. Ar₄P· radicals formed by the reaction: Ar₄P⁺ + e_aq⁻ → Ar₄P· have a maximum absorption at 305 nm [ε₃₀₅ = (9400 ± 300) dm³ mol⁻¹ cm⁻¹] and decays by second-order kinetics with the rate constant 2k = (2·7 ±0·4) × 10⁹ dm³ mol⁻¹ s⁻¹. H atoms and OH radicals form transient adducts to the phenyl groups of the Ar₄P⁺ ion with the rate constants of (1·5 ± 0·3) × 10⁹ dm³ mol⁻¹ s⁻¹ and (3·0±0·3) × 10⁹ dm³ mol⁻¹ s⁻¹, respectively. Both adducts have broad absorption spectra at 300≈380 nm (λ_max = 340 nm) with the molar extinction coefficients ε₃₄₀ = 5400±300 dm³ mol⁻¹ cm⁻¹ for the H adduct and ε₃₄₀ = 3500±200 dm³ mol⁻¹ cm⁻¹ for the OH adduct.     

Pulse radiolysis study of dithio-oxamide in aqueous solutions

The reactions of e⁻ _aq, H-atoms, OH radicals and some one electron oxidants and reductants were studied with dithio-oxamide (DTO) in aqueous solutions using pulse radiolysis technique. The transient species formed by the reaction of e⁻ _aq with DTO at pH 6.8 has an absorption band with λ _max at 380 nm and is reducing in nature. H-atom reaction with DTO at pH 6.8 also produced the same transient species. The semi-reduced species was found to be neutral indicating that the electron adduct gets protonated quickly. However at pH 1, the species produced by H-atom reaction had a different spectrum with λ _max at 360 and 520 nm. Reaction of acetone ketyl radicals and CO₂ ⁻ radicals with DTO at pH 6.8 gave transient spectra which were identical to that obtained by e⁻ _aq reaction. However at pH 1, the spectrum obtained by the reaction of acetone ketyl radicals with DTO was similar to that obtained by H-atom reaction at that pH. The transient species formed by OH radical reaction with DTO in the pH range 1–9.2 also has two absorption maxima at 360 and 520 nm. This spectrum was identical with the spectrum obtained by H-atom reaction at pH 1. This means that all these radicals viz. OH, H-atom and (CH₃)₂COH radicals react with DTO at pH 1 by H-abstraction mechanism. The transient species produced was found to be sensitive to the presence of oxygen. One-electron oxidizing radicals such as Br₂ ^−· and SO₄ ^−· radicals reacted with DTO at neutral pH to give the same species as produced by OH radical reaction having absorption maxima at 360 to 520 nm. At acidic pHs, only Br₂ ^−· and Cl₂ ^−· radicals were able to oxidize DTO to give the same species as produced by OH radical reaction. The semioxidized species is a resonance stabilized species with the electron delocalized over the-N-C-S bond. This species was found to be neutral and non-oxidizing in nature.     

Pulse radiolysis of pyridine and methylpyridines in aqueous solutions

The radicals formed from pyridine, 3-methylpyridine, 3,5-dimethylpyridine, 2,6-dimethylpyridine and 2,4,6-trimethylpyridine by attack of H, e^-_aq, OH and O^•- in acqueous solutions were investigated by pulse radiolysisin the pH-range 1–13.8. The UV-vis. absorption spectra as well as the formation and decay kinetics for the protonated and unprotonated forms of the methylpyridine radicals studied are presented. The pK_a-values for the OH-adducts were determined.     

Pulse radiolysis of adrenaline in acid aqueous solutions

Pulse radiolysis of adrenaline in acid aqueous solutions (pH 1–3) was carried out. The rate constants for the reactions of adrenaline with H and OH were determined: k(H + adr.) = (0·9±0·1) × 10⁹ dm³ mol⁻¹ s⁻¹; k(OH + adr.) = (1·65±0·15) × 10¹⁰ dm³ mol⁻¹ s⁻¹. The H-adduct of adrenaline has two λ_max, at 280 and 355 nm, with ϵ₂₈₀ = 420 m² mol⁻¹ and ϵ₃₅₅ = 390 m² mol⁻¹, which disappears according to a first order reaction, k₁ = 1·4 × 10³ s⁻¹. The spectra formed by OH attack was assigned to the corresponding benzoxy radical with absorption maxima at 285 and 365 nm and ϵ₂₈₅ = 620 m² mol⁻¹ and ϵ₃₆₅ = 105 m² mol⁻¹. Due to the overlapping of the intermediates, no decay kinetics could be obtained.     

Gamma radiolysis of erythrosine dye in aqueous solutions

Beryllium-7, mainly measured via γ-spectrometry, is used as a (natural) radiotracer for education and science. For activities?<?0.1 Bq and samples containing also longer-lived ¹⁰Be, accelerator mass spectrometry (AMS) is the method-of-choice. We demonstrate that ⁷Be and ¹⁰Be can be quantified at the Dresden AMS facility on the same prepared BeO. Detection limits (⁷Be) are?~?0.6 mBq. Samples as small as tens of millilitres of rainwater can be chemically processed (after acidification) within a few hours without expensive and slow ion exchange. Isobar (⁷Li) suppression by chemistry and AMS is sufficient to guarantee for an ultrasensitive, cheap, and fast detection method for ⁷Be allowing high sample throughput.

     

The degradation of bentazone and chlorotoluron in aqueous solutions by gamma radiation. Biodegradability and toxicity /to Tubifex tubifex/ of radiolysis products

Model aqueous solutions of bentazone and chlorotoluron /herbicide concentration=200 mg.l^–1/ were irradiated with and without simultaneous aeration by -doses in the range 0–52.8 kGy. The degradation of herbicides was studied by UV spectroscopy and chronometric method of herbicide residues determination. The effect of radiation on the biodegradability of bentazone and chlorotoluron solutions were evaluated on the basis of BOD₅/COD ratio determination and toxicity of nondiluted model solutions irradiated by doses in the given range to worms Tubifex tubifex was determined.     

Neutral thallium clusters in aqueous solutions. Pulse radiolysis study

The formation of neutral Tl₂ (λ_max = 390 nm) and Tl₄ (λ_max = 360 nm) clusters in dilute aqueous solutions of Tl₂SO₄ containing formate ions was found by pulse radiolysis. The rate constants for the recombination of Tl⁰ atoms and Tl₂ clusters are equal to 1.5·10¹⁰ L mol⁻¹ s⁻¹ and 1.0·10¹⁰Lmol⁻¹ s⁻¹ (±30%), respectively, and the extinction coefficient of Tl₂ at 390 nm is −6.0·10³ L mol⁻¹ cm⁻¹ Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2367–2369, December, 1999.     

4-氯酚稀水溶液的脉冲辐解研究

利用脉冲电子束进行了多种条件下4－氯酚稀水溶液的脉冲辐解研究,对其瞬态光谱中的主要吸收峰作了归属,并初步考察了这些瞬态物种的生长、衰减等行为,研究表明,·OH基与4－氯酚在碱性条件下反应生成氯代酚氧基,速率常数为4.14×10^9L/(mol·s),在酸性条件下要经过OH-adducts;H原子与4-氯酚反应生成H-adducts的速率常为2.0×10^9L/(mol·s),产物可通过双分子二级反应逐步脱氯;eaq^-可直接从4-氯酚分子夺氯,反应速率常数为1.82×10^9/L(mol·s)。     

Effect of iso-propanol on the radiolysis of aqueous solutions of periodate

The -radiolysis of IO ₄ ^– in aqueous solution and binary solutions containing iso-propanol has been studied as a function of reactant concentration and absorbed dose. The disappearance of periodate ion in the presence of alcohol is found to be higher as compared to that observed in the pure system. The trend in the G-values determined at various combinations of the reactant concentrations suggests the occurrence of a chain reaction in the radiolytic process.