Kinetics of Tc(VII) reduction with diformylhydrazine in a nitric acid solution in the presence of U(VI) ions

Мұқаба

Дәйексөз келтіру

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Аннотация

The Tc(VII) reduction with 1,2-diformylhydrazine in nitric acid solutions in the presence of U(VI) was studied spectrophotometrically. The reduction of Tc(VII) to Tc(IV) through the intermediate form of Tc(V) was found. The optical spectra were decomposed into two components by methods of mathematical processing. Kinetic curves have S-like appearance. It has been suggested that the induction period is associated with the Tc(V) formation. The kinetic equation of the Tc(IV) formation in the studied conditions was obtained. It was found that the rate of Tc(V) formation increases with an increase in the 1,2-diformylhydrazine, U(VI), and initial Tc(VII) concentrations and in the temperature but decreases with an increase in the nitric acid concentration. The reaction rate constants and partial orders of reaction components were found on the basis of the obtained data.

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Авторлар туралы

K. Dvoeglazov

AO Proryv; Bochvar High-Tech Institute of Inorganic Materials

Хат алмасуға жауапты Автор.
Email: dkn@pnproryv.ru
Ресей, pl. Akademika Dollezhalya 1, bld. 7, office 307, Moscow, 107140; ul. Rogova 5a, Moscow, 123060

E. Filimonova

Bochvar High-Tech Institute of Inorganic Materials

Email: dkn@pnproryv.ru
Ресей, ul. Rogova 5a, Moscow, 123060

L. Podrezova

Bochvar High-Tech Institute of Inorganic Materials

Email: dkn@pnproryv.ru
Ресей, ul. Rogova 5a, Moscow, 123060

E. Pavlyukevich

Bochvar High-Tech Institute of Inorganic Materials

Email: dkn@pnproryv.ru
Ресей, ul. Rogova 5a, Moscow, 123060

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2. Fig. 1. Absorption spectra at different time intervals after the start of the experiment. [Tc] = 45 mg/l, [HNO3] = 0.5 mol/l, [U(VI)] = 20 g/l, [DPG] = 0.5 mol/l, 30°C. Time from the start of the experiment, min: 1 – 10, 2 – 30, 3 – 40, 4 – 60, 5 – 120, 6 – 150 min.

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3. Fig. 3. Lorentzian approximation of the spectrum recorded 150 min after the addition of the reducing agent. [Tc(VII)] = 30 mg/l, [HNO3] = 1.0 mol/l, [DPG] = 0.1 mol/l at a temperature of 40°C.

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4. Fig. 4. Dependence of optical density at a wavelength of 484 nm on time at [Tc] = 100 mg/l, [HNO3] = 1.0 mol/l, 30°C and the initial concentration of DPG, mol/l: 1 – 0.1, 2 – 0.3, 3 – 0.5, 4 – 0.7, 5 – 0.9.

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5. Fig. 5. Comparison of kinetic curves for different compositions of the DPG stock solution, [Tc] = 100 mg/l, [DPG] = 0.5 mol/l, 30°C. Concentration of HNO3 in the DPG stock solution, mol/l: 1 – 0.1, 2 – 0.5, 3 – 1.0.

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6. Fig. 6. Dependence of optical density on time at different concentrations of nitric acid. [Tc] = 100 mg/l, [DPG] = 0.5 mol/l, 30°C; [HNO3], mol/l: 1 – 0.5, 2 – 1.0, 3 – 1.4, 4 – 1.7, 5 – 2.2.

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7. Fig. 7. Dependence of optical density on time at different concentrations of UO2 2+ ions, [Tc] = 30 mg/l, [HNO3] = 0.5 mol/l, [DPG] = 0.5 mol/l, 30°C; [U], g/l: 1 – 5, 2 – 20, 3 – 40, 4 – 60.

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8. Fig. 8. Graphic transformation of kinetic curves in semilogarithmic coordinates at [Tc] = 30 mg/l, [DPG] = 0.5 mol/l, [U] = 20 g/l, temperature 30°C and [HNO3], mol/l: 1 – 0.5, 2 – 0.75, 3 – 1.0.

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9. Fig. 2. Simulated spectral profiles of technetium at [Tc] = 30 mg/L, [HNO3] = 0.5 mol/L, [DPG] = 0.5 mol/L and 30°C. 1, 1' – component 1; 2, 2’ – component 2; unprimed 5, primed 20 g/L uranium.

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