Reaction of nitrate ion with formic acid in the presence of uranium

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Abstract

The reaction of nitric acid with formic acid, including uranium-containing solutions, was studied. Empirical equations for the dependence of the induction period duration (τ) on the concentrations of reagents and temperature were determined. The dependence of τ on the concentration of formic acid is exponential. The effect of uranium concentration on τ in denitrated solutions becomes noticeable only at temperatures lower than 60°C. The main factor affecting the completeness of denitration is the molar ratio [formic acid] : [NO3]¯. Starting with the molar ratio of ≥3, uranium-containing solutions are denitrated at 90°C in an hour almost quantitatively. The resulting uranyl formate is partially precipitated. The initial stage of the reaction is accompanied by violent gas evolution. At 90°C, ~80% of the gas volume is released at this stage (about 10 s), whereas at 40°C, only ~10%.

The reaction of nitric acid with formic acid, including uranium-containing solutions, was studied. Empirical equations for the dependence of the induction period duration (τ) on the concentrations of reagents and temperature were determined. The dependence of τ on the concentration of formic acid is exponential. The effect of uranium concentration on τ in denitrated solutions becomes noticeable only at temperatures lower than 60°C. The main factor affecting the completeness of denitration is the molar ratio [formic acid] : [NO3]¯. Starting with the molar ratio of ≥3, uranium-containing solutions are denitrated at 90°C in an hour almost quantitatively. The resulting uranyl formate is partially precipitated. The initial stage of the reaction is accompanied by violent gas evolution. At 90°C, ~80% of the gas volume is released at this stage (about 10 s), whereas at 40°C, only ~10%.

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L. V. Krasnikov

Khlopin Radium Institute

Author for correspondence.
Email: lkrasnikov@khlopin.ru
Russian Federation, 2-i Murinskii pr. 28, St. Petersburg, 194021

A. A. Lumpov

Khlopin Radium Institute

Email: lkrasnikov@khlopin.ru
Russian Federation, 2-i Murinskii pr. 28, St. Petersburg, 194021

N. A. Semenova

Khlopin Radium Institute

Email: lkrasnikov@khlopin.ru
Russian Federation, 2-i Murinskii pr. 28, St. Petersburg, 194021

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3. Fig. 1. Dependence of the completeness of denitration on the molar excess of formic acid. T = 90°C, 1 h

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4. Fig. 2. Dependence of the induction period duration on the formic acid concentration. T = 90°C, 1.7–3 mol/l HNO3. exp ‒ experiment; (8) – calculation using equation (8); (9) – calculation using equation (9); (11) – calculation using equation (11)

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5. Fig. 3. Dependence of the induction period on the temperature and the amount of “free” nitrate ion. Uranium concentration 600 g/l

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6. Fig. 4. Dependence of the induction period on the uranium concentration at a constant total concentration of [NO3 –] 6.72 mol/l. The molar ratio [NO3 –] : [HCOOH] = 1 : 3

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7. Fig. 5. Dependence of nitrate ion consumption on the ratio [HCOOH] : [NO3 –] for 1 hour. T = 90°C. Uranium concentration 400 g/l

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8. Fig. 6. Dependence of the amount of uranium in the precipitate on its initial concentration in the reaction mixture. T = 90°C, [HCOOH] : [NO3 –] = 4

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9. Fig. 7. Dependence of the volume of released gas on the temperature and duration of the reaction. 0.5 mol/l HNO3. Uranium concentration 800 g/l, [HCOOH] : [NO3 –] = 4

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