A new detection method of99Tc by nuclear excitation

A new nuclear excitation process,⁹⁹Tc (, )^99mTc reaction, was applied for the first time to radioactivation analysis of technetium. Bremsstrahlung irradiation of⁹⁹Tc samples gave the reaction product^99mTc which emits -ray measurable with ease by a semiconductor detector. The production rate of^99mTc per g⁹⁹Tc was linearly correlated with the flux of bremsstrahlung. The detection limit of⁹⁹Tc was estimated to be nanogram order (0.63 Bq⁹⁹Tc) under the optimum irradiation condition. Possible interference by¹⁰⁰Ru(, p)^99mTc reaction was also studied, which could be discriminated from the (, ) reaction by simultaneously occurring⁹⁸Ru (, p)⁹⁷Ru reaction.     

Recoil implantation reaction in geometrical isomers of tris/benzoylacetonato/chromium/III/

Hot atom chemical reaction by⁵⁰Cr/n, /⁵¹Cr and⁵²Cr/, n/⁵¹Cr reactions, and recoil implantation reaction by⁵¹V/p, n/⁵¹Cr reaction were investigated using geometrical isomers /mer and fac/ of tris/benzoylacetonato/ chromium/III/ /Cr/ba/₃/. The production of counter isomer was observed for both mer- and fac-targets, although the yield of labelled parent isomer was larger. The observed mer/fac yield ratio suggests that the main formation mechanism of⁵¹Cr/ba/₃ is the reaction of ba^– and Cr/ba/ ₂ ⁺ which has the same geometrical configuration of target complex, and the substitution reaction of central metal atom by recoil⁵¹Cr. Furthermore, implantation gave rise to a much higher yield of labelled Cr/ba/₃ compared to the case of in situ nuclear recoils.     

The kinetics of the oxidation-reduction reaction between uranium(VI) and titanium(III) in HCl solution

The oxidation-reduction reaction between U(VI) and Ti(III) in HCl solution was studied spectrophotometrically. The reaction is second-order at all concentrations of reactants, HCl, ferrous chloride and mannitol used in this work. In 5M HCl the rate constantk increases with increasing Ti(III) concentration, whereas it decreases with increasing U(VI) concentration, with increasing HCl concentration from 1.00M to 7.17M and increases thereafter from 7.17M to 11.79M. The addition of mannitol causes a consistent decrease in the rate of reaction, whereas ferrous chloride has no effect. The activation energy for this oxidation-reduction reaction was 47.90±0.11 kJ·mol^–1. The values of H , G and S were 45.40±0.11 kJ·mol^–1, 72.50±0.17 kJ·mol^–1 and –91.10±0.22J·k^–1·mol^–1, respectively. The mode of reaction is discussed in the light of kinetic results.     

Kinetics and mechanisms of the reactions of thiosulphato-amine complexes of cobalt(III). Part II. Base hydrolysis of the bis(ethylenediamine)thiosulphatocobalt(III) ion

Summary Base hydrolysis of the bis(ethylenediamine)thiosulphatocobalt(III) was investigated spectrophotometrically between 35 and 65 °C and with base concentrations (NaOH) up to 2.0 mol dm^–3. The hydrolysis consists of a one-stage reaction, followed by a slow dechelation step, and then by a fast ligand loss. The reaction is base-dependent. The products of the reaction are an equilibrium mixture ofcis- andtrans-Coen₂ (OH) ₂ ⁺ . Activation parameters for the reaction as determined by the Eyring equation, are H=77.8±4.6 kJ mol^–1 and S=–75±20 JK^–1 mol^–1.     

Reactions of Caryophyllene 4β,5α-Epoxide with Carbonyl Compounds on Clay

Products of reaction between caryophyllene 4,5-epoxide and carbonyl compounds (acrolein, crotonaldehyde, -methacrolein, and acetone) were synthesized on clay. Two diastereomers in reaction with each aldehyde and a single isomer with acetone were obtained. In reaction of the epoxide with acetone an isomerization product was isolated, 4,4,9-trimethyltricyclo[6.2.2.0^{1 , 5}]dodec-9-en-2-ol that was unknown before.     

Reactions of Peroxy Radicals with Hydrocarbons and Alcohols: Transition State Geometry and the Polar Effect

The reaction EtOO + EtH EtOOH + Et was studied by the intersecting parabolas method and calculated using density functional theory. The interatomic C–H, O–H, and C–O distances of the transition state for this reaction were calculated using these methods. The formulas for calculating these distances from experimental data were obtained. Similar calculations and comparisons were carried out for the reaction EtOO + MeCH₂OH EtOOH + MeCHOH. The polar effect of the hydroxy groups on the transition state manifested itself in a decrease in the activation energy and in the formation of a nonlinear structure of the transition state. An empirical formula for estimating the C–H–O angle in the transition state from the enthalpy and activation energy was derived.     

Kinetic Determination of Iodide Traces Based on the Manganese(III) Metaphosphate–Arsenic(III) Reaction in the Presence of Orthophosphoric Acid

The kinetics of the iodide-catalyzed Mn(III) metaphosphate–As(III) reaction was studied in the presence of orthophosphoric acid. The reaction rate was followed spectrophotometrically at 516nm. It was established that orthophosphoric acid increased the reaction rate and that the extent of the non-catalytic reaction was extremely small. A kinetic equation was postulated and the apparent rate constant calculated. The dependence of the reaction rate on temperature was investigated and the energy of activation and other kinetic parameters determined. Iodide was determined under the optimal experimental conditions in the range 0.6–2.5ng·mL^–1 with a relative standard deviation of up to 6.7% and a detection limit of 0.12ngmL^–1. The effect of foreign ions on the accuracy of the determinations was also investigated.     

Absolute rate constants for reactions of free radicals in the high-temperature photolysis of formamide vapor. II. Amino radicals

The rotating-sector method has been applied to the photoinitiated radical-chain decomposition of formamide at 300°C to measure the rate constant for the bimolecular disappearance of NH₂ radicals. The decomposition is propagated by the reactions (1) (2) Conditions were chosen so that reaction (1) was rate controlling and NH₂ the terminating radical. A flow system was employed with C₂F₆ as a carrier gas at a pressure of 300 Tort, and the chain reaction was initiated by the photolysis of either formamide or NH₃. A value of 4.7(±2.0) × 10¹⁰ (M ·sec)^?1 was estimated for the termination reaction (3) and a value of 8.4 × 10⁶ (M ·sec)^?1 for reaction (1) in the same system, both at 300°C.     

Production of no carrier added residue free22Na

A method for the production of no carrier added and residue free²²Na, was developed via the²⁴Mg/d, /²²Na nuclear reaction applying 14 MeV deuterons and a high current Mg–Cu target. The yield for the reaction target. The yield for the reaction was measured and the chemical separation performed using a Dowex 50WX8 resin in H⁺ form. The overall yield was higher than 98%. Residue could not be detected. All experiments were carried out at IEN's CV-28 cyclotron.     

MCSCF reaction-path energetics and thermal rate-constants for the reaction of3NH with H2

Summary The intrinsic reaction-path, reactants, transition state and products for the reaction of NH (^3–)+H₂ (¹ _g ⁺ ) NH₂ (²B₁)+H (²S) involving the lowest triplet electronic state of NH₃ were calculated using multi-configuration (MC) SCF methods. The calculated change of internal energy for the reaction of 11.0 kcal mol^–1 agrees with the experimental value within 2 kcal mol^–1. The barrier to reaction is 23.4 kcal mol^–1 high. The harmonic MCSCF reaction-path potential was calculated and canonical variational transition state theory calculations of the rate constants performed over a temperature range from 400 to 2500 K. The computed rate constants are generally two orders of magnitude smaller than those of the comparable reaction of OH with H₂, whereas those of the reverse reaction are by a factor of 20 larger than those of OH₂ with H.     

Specific radiation and recoil energy effects in recoil implantation reaction of51Cr in metal acetylacetonates

In recoil implantation reaction of⁵¹Cr in Cr/acac/₃ a polymer component which was sensitive to radiation dose was found. However, a retention type component⁵¹Cr/acac/₃ was not so sensitive to radiation dose. A remarkable dependence of the yield of⁵¹Cr/acac/₃ on recoil energy was found in the range 10²–10⁶ eV in recoil implantation using a thin film technique. This suggests a special role of implantation reaction in solids.     

On the thermal decomposition of COS

The thermal dissociation of COS was investigated in shock waves with argon as carrier gas. The concentration was varied between 0.05 and 0.5% COS in argon, the total density from 2.5 × 10^?5 mole/cm³ to 2.5 × 10^?3 mole/cm³. Temperatures between 1500°K and 3100°K were applied. For the reaction the rate constant was found to be in the low pressure range of the unimolecular reaction and in the high pressure range.     

Nucleophilic Aromatic Substitution Between Halogenated Benzene Dopants and Nucleophiles in Atmospheric Pressure Photoionization

In a preceding work with dopant assisted-atmospheric pressure photoionization (DA-APPI), an abundant ion at [M + 77]⁺ was observed in the spectra of pyridine and quinoline with chlorobenzene dopant. This contribution aims to reveal the identity and route of formation of this species, and to systematically investigate structurally related analytes and dopants. Compounds containing N-, O-, and S-lone pairs were investigated with APPI in the presence of fluoro-, chloro-, bromo-, and iodobenzene dopants. Computational calculations on a density functional theory (DFT) level were carried out to study the reaction mechanism for pyridine and the different halobenzenes. The experimental and computational results indicated that the [M + 77]⁺ ion was formed by nucleophilic aromatic ipso-substitution between the halobenzene radical cation and nucleophilic analytes. The reaction was most efficient for N-heteroaromatic compounds, and it was weakened by sterical effects and enhanced by resonance stabilization. The reaction was most efficient with chloro-, bromo-, and iodobenzenes, whereas with fluorobenzene the reaction was scarcely observed. The calculated Gibbs free energies for the reaction between pyridine and the halobenzenes were shown to increase in the order I < Br < Cl < F. The reaction was found endergonic for fluorobenzene due to the strong C–F bonding, and exergonic for the other halobenzenes. For fluoro- and chlorobenzenes the reaction was shown to proceed through an intermediate state corresponding to [M + dopant]⁺, which was highly stable for fluorobenzene. For the bulkier bromine and iodine, this intermediate did not exist, but the halogens were shown to detach already during the approach by the nucleophile.

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The kinetics of the reaction of iodine with hydrazine as studied by pulse radiolysis

Pulse radiolysis was utilized to study the iodine — hydrazine reaction in aqueous solutions of pH3 to 7, at I^– concentrations of 0.02 to 0.34M, and a constant ionic strength of 0.35M. The reaction rate was found to be proportional to [H⁺]^–1 and [I^–]^–1. Experimental results support the assumption that the rate-determining step is the reaction of I₂ with N₂H₄ with a rate constant K1.2×10⁷ M^–1s^–1.     

Activation analysis for technetium-99 by the use of a neutron-excitation reaction

The formation of^99mTc was observed when⁹⁹Tc was irradiated by reactor neutrons as a result of the⁹⁹Tc(n, )^99mTc reaction. A good linearity was observed between the activities of^99mTc produced and⁹⁹Tc irradiated. The cross section of the excitation reaction was estimated to be 0.24 b. The application of the nuclear excitation reaction to the activation analysis for low level⁹⁹Tc was studied.     

Preparation and application of237U for the study of heterogeneous isotope exchange on an ion exchanger

The possibility of preparation of²³⁷U by the²³⁸U(, n)²³⁷U reaction, realized by irradiation of UO₃ on the microtron, has been verified. The relation between yields for (, n) and (, f) reaction was determined. The activated uranium was separated from fission products by extraction into diethyl ether.²³⁷U was used for the study of the kinetics of heterogeneous isotope exchange in the system aqueous solution of UO₂(NO₃)₂ — ion exchanger Wofatit CA-20 in UO ₂ ²⁺ form. The experimental results were evaluated by a model based on particle diffusion with simultaneous isotope exchange between two uranium forms in the ion exchanger.     

Photoinduced chemiluminescence in salicylaldehyde hydrazone solution

Simultaneously with the chemiluminescent reaction of salicylaldehyde hydrazone (G) oxidation by hypochlorite, the competing chemiluminescent reaction of G with the hydroxide ion occurs in alkaline media. The former reaction is accompanied by green chemiluminescence, whereas the latter, with blue chemiluminescence. The estimation of the rate constant for the bimolecular reaction G + OH^– gives the value 2×10⁵ l mol^–1 s^–1. The necessary condition for appearance of chemiluminescence upon interaction of G with OH^– is the preliminary illumination of the solution of G with light at a wavelength of 400–540 nm, which is accompanied by the formation of an acoplanar quinonoid isomer of G interacting with the hydroxide ion. The height of the energetic barrier for transition of G molecules from the illuminated to the dark state is 18 kcal mol^–1.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 2, 2005, pp. 129–134.Original Russian Text Copyright © 2005 by Tsaplev.This revised version was published online in April 2005 with a corrected cover date.     

Chromium(VI), chromium(V) and chromium(IV) oxidation of 12-tungstocobaltate(II)

The reaction between Cr^VI and 12-tungstocobaltate(II) was carried out in 2.0 mol dm^–3 HCl and followed a simple second order rate law. The reaction was catalysed by hydrogen ion due to the formation of active H₂CrO₄ and was inhibited by chloride ion as, in its presence, conversion of the active species into inactive chlorochromate occurs. Chromium(V) and chromium(IV) were generated in situ by the use of Cr^VI—V^IV or Cr^VI—2-ethyl-2-hydroxybutyric acid and Cr^VI—i-PrOH reactions respectively, and the oxidation of 12-tungstocobaltate(II) by these atypical oxidation states, was also studied. The rate constants for the oxidation of 12-tungstocobaltate(II) by Cr^VI, Cr^V and Cr^IV were found to be in the ratio 1:1.2:5.2 respectively. The ionic strength did not affect the reaction, while decrease in the solvent polarity increased the rate of the reaction. The activation parameters were also determined and the values H , G and S were found to be 52.4 ± 6 kJ mol^–1, 100.8 ± 7 kJ mol^–1, –151.7 ± 10 J K^–1 mol^–1 respectively, supporting the mechanism proposed.     

Acid-Base Properties of Substituted 9-Chloroacridines

Ionization constants (pKBH⁺) of eleven substituted 9-chloroacridines in water-ethanol mixtureswere measured by potentiometric titration at 25°C. The correlation between pKBH⁺, the Hammett constants was established, and the reaction parameter was evaluated. The sensitivity of the reaction center tothe effect of substituents is low. Annelation of the heterocycle decreases the sensitivity of the reaction center to the structural changes in the molecule.