Brines formed by multi-salt deliquescence

Technical Report · Fri Nov 04 04:00:00 EST 2005

DOI:https://doi.org/10.2172/928172· OSTI ID:928172

Carroll, S; Rard, J; Alai, M; Staggs, K

The FY05 Waste Package Environment testing program at Lawrence Livermore National Laboratory focused on determining the temperature, relative humidity, and solution compositions of brines formed due to the deliquescence of NaCl-KNO{sub 3}-NaNO{sub 3} and NaCl-KNO{sub 3}-NaNO{sub 3}-Ca(NO{sub 3}){sub 2} salt mixtures. Understanding the physical and chemical behavior of these brines is important because they define conditions under which brines may react with waste canister surfaces. Boiling point experiments show that NaCl-KNO{sub 3}-NaNO{sub 3} and NaCl-KNO{sub 3}-NaNO{sub 3}-Ca(NO{sub 3}){sub 2} salt mixtures form brines that transform to hydrous melts that do not truly 'dry out' until temperatures exceed 300 and 400 C, respectively. Thus a conducting solution is present for these salt assemblages over the thermal history of the repository. The corresponding brines form at lower relative humidity at higher temperatures. The NaCl-KNO{sub 3}-NaNO{sub 3} salt mixture has a mutual deliquescence relative humidity (MDRH) of 25.9% at 120 C and 10.8% at 180 C. Similarly, the KNO{sub 3}-NaNO{sub 3} salt mixture has MDRH of 26.4% at 120 C and 20.0% at 150 C. The KNO{sub 3}-NaNO{sub 3} salt mixture salts also absorb some water (but do not appear to deliquesce) at 180 C and thus may also contribute to the transfer of electrons at interface between dust and the waste package surface. There is no experimental evidence to suggest that these brines will degas and form less deliquescent salt assemblages. Ammonium present in atmospheric and tunnel dust (as the chloride, nitrate, or sulfate) will readily decompose in the initial heating phase of the repository, and will affect subsequent behavior of the remaining salt mixture only through the removal of a stoichiometric equivalent of one or more anions. Although K-Na-NO{sub 3}-Cl brines form at high temperature and low relative humidity, these brines are dominated by nitrate, which is known to inhibit corrosion at lower temperature. Nitrate to chloride ratios of the NaCl-KNO{sub 3}-NaNO{sub 3} salt mixture are about NO{sub 3}:Cl = 19:1. The role of nitrate on corrosion at higher temperatures is addressed in a companion report (Dixit et al., 2005).

• Research Organization: Lawrence Livermore National Laboratory (LLNL), Livermore, CA
• Sponsoring Organization: USDOE
• DOE Contract Number: W-7405-ENG-48
• OSTI ID: 928172
• Report Number(s): UCRL-TR-217062
• Country of Publication: United States
• Language: English

Related Subjects

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES
ANIONS
BOILING POINTS
BRINES
CHLORIDES
CONTAINERS
CORROSION
DUSTS
ELECTRONS
HEATING
HUMIDITY
LAWRENCE LIVERMORE NATIONAL LABORATORY
MIXTURES
NITRATES
REMOVAL
TESTING
WASTES
WATER