A STUDY OF EQUILIBRIA INVOLVED BETWEEN DAREX OFF-GASES AND SOLUTIONS. Annual Report No. 1 for December 1, 1958 through July 31, 1959

Technical Report · Sat Oct 31 04:00:00 EST 1959

OSTI ID:4219406

Orr, C Jr; Kordecki, M C; Gladden, J K; Young, C T

In the Darex process, aqua regia is used to dissolve the materials of spent reactor fuel elements. For economic reasons, it is desirable to recover the off-gases from the dissolving process, especially the chlorine, in acid solutions that can be recycled in the system. This project was undertaken to develop a method of analyzing the off-gases and to determine their solubility in various concentrations of hydrochloric acid, nitric acid, and aqua regia at several temperatures. Work was concentrated on the development of a precise method for the quantitative analysis of gaseous mixtures oontaining some or all of the following gases: NO, N/sub 2/O, NO/sub 2/(N/sub 2/O/sub 4/), NOCl, HCl, Cl/ sub 2/, and water vapo r. The initial emphasis was placed on gas chromatography, but no combination of columns and conditions was found by which accurate results for all these gases could be obtained. Analyses by spectrophotometric methods appeared at first to be unsatisfaciory because of the masking by NO/sub 2/ and C1/ sub 2/ in the visible and the ultraviolet range, the absorption by water in the infrared region, and the absence of absorption by C1/sub 2/ in the infrared region. Experiments have now shown, however, that water vapor does not entirely mask the other components. A complete analysis can be accomplished if, after the gaseous mixture has been scanned with an infrared spectrophotometer, the separation of chlorine is effected by dissolving the mixture in CCl/sub 4/ and shaking it with water. Only the chlorine remains in the CCl/sub 4/ layer and can be analyzed spectrophotometrically in the ultraviolet or visible region. Preliminary experiments of this type have shown how the gases from aqua regia at atmospheric pressure vary vith time. Samples taken 20 minutes after mixing showed the presence of HCl in the gas phase and gave an indication of some water vapor. Samples taken after 70, 120, and 205 minutes did not reveal HCl but gave progressively larger NOCl peaks and showed a yellow color, indicating the presence of chlorine. After 48 hours the sample peaks were essentially the same as those from the 205-minute sample. (auth)

• Research Organization: Georgia Inst. of Tech., Atlanta. Engineering Experiment Station
• NSA Number: NSA-13-019978
• OSTI ID: 4219406
• Report Number(s): AECU-4304
• Country of Publication: United States
• Language: English

Related Subjects

ACIDITY
CARBON TETRACHLORIDE
CHEMISTRY
CHLORIDES
CHLORINE
CHROMATOGRAPHY
DAREX PROCESS
FUEL ELEMENTS
GASES
HYDROCHLORIC ACID
INFRARED RADIATION
NITRIC ACID
NITROGEN OXIDES
PHOTOMETRY
QUANTITATIVE ANALYSIS
RECOVERY
SOLUBILITY
SOLUTIONS
SPECTROSCOPY
ULTRAVIOLET RADIATION
VAPORS
WATER