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Title: Results from Boiling Temperature Measurements for Saturated Solutions in the Systems NaCl + Ca(NO3)2 + H2O, NaNO3 + KNO3 + H2O, and NaCl + KNO3 + H2O, and Dry Out Temperatures for NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O

Abstract

Boiling temperature measurements have been made for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O and NaNO{sub 3} + KNO{sub 3} + H{sub 2}O at three selected salt ratios and for NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O over the full composition range. The maximum boiling temperature found for the NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O system is 164.7 {+-} 0.6 C, and the composition is estimated to occur at x(Ca(NO{sub 3}){sub 2}) {approx} 0.25. Experiments were also performed for the five component NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O mixtures with the molar ratio of NaCl:NaNO{sub 3}:KNO{sub 3} held essentially constant at 1:0.9780:1.1468 as the solute mole fraction of Ca(NO{sub 3}){sub 2}, x(Ca(NO{sub 3}){sub 2}), was varied between 0 and 0.25. The NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O system forms low melting mixtures and thus boiling temperatures for saturated were not determined. Instead, the temperatures corresponding to the cessation of boiling (i.e., dry out temperatures) of these liquid mixtures were determined. These dry out temperatures range from {approx} 300 C when x(Ca(NO{sub 3}){sub 2}) = 0 to {ge}more » 400 C when x(Ca(NO{sub 3}){sub 2}) = 0.20 and 0.25. The investigated mixture compositions correspond to some of the major mineral assemblages that are predicted to control the deliquescence relative humidity of salts formed by leaching dust samples from the proposed nuclear repository at Yucca Mountain, Nevada.« less

Authors:
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
889972
Report Number(s):
UCRL-TR-217415
TRN: US0604512
DOE Contract Number:
W-7405-ENG-48
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; 58 GEOSCIENCES; 54 ENVIRONMENTAL SCIENCES; BOILING; DUSTS; HUMIDITY; LEACHING; MELTING; MIXTURES; SOLUTES; TEMPERATURE MEASUREMENT; YUCCA MOUNTAIN

Citation Formats

Rard, J A. Results from Boiling Temperature Measurements for Saturated Solutions in the Systems NaCl + Ca(NO3)2 + H2O, NaNO3 + KNO3 + H2O, and NaCl + KNO3 + H2O, and Dry Out Temperatures for NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O. United States: N. p., 2005. Web. doi:10.2172/889972.
Rard, J A. Results from Boiling Temperature Measurements for Saturated Solutions in the Systems NaCl + Ca(NO3)2 + H2O, NaNO3 + KNO3 + H2O, and NaCl + KNO3 + H2O, and Dry Out Temperatures for NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O. United States. doi:10.2172/889972.
Rard, J A. Tue . "Results from Boiling Temperature Measurements for Saturated Solutions in the Systems NaCl + Ca(NO3)2 + H2O, NaNO3 + KNO3 + H2O, and NaCl + KNO3 + H2O, and Dry Out Temperatures for NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O". United States. doi:10.2172/889972. https://www.osti.gov/servlets/purl/889972.
@article{osti_889972,
title = {Results from Boiling Temperature Measurements for Saturated Solutions in the Systems NaCl + Ca(NO3)2 + H2O, NaNO3 + KNO3 + H2O, and NaCl + KNO3 + H2O, and Dry Out Temperatures for NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O},
author = {Rard, J A},
abstractNote = {Boiling temperature measurements have been made for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O and NaNO{sub 3} + KNO{sub 3} + H{sub 2}O at three selected salt ratios and for NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O over the full composition range. The maximum boiling temperature found for the NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O system is 164.7 {+-} 0.6 C, and the composition is estimated to occur at x(Ca(NO{sub 3}){sub 2}) {approx} 0.25. Experiments were also performed for the five component NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O mixtures with the molar ratio of NaCl:NaNO{sub 3}:KNO{sub 3} held essentially constant at 1:0.9780:1.1468 as the solute mole fraction of Ca(NO{sub 3}){sub 2}, x(Ca(NO{sub 3}){sub 2}), was varied between 0 and 0.25. The NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O system forms low melting mixtures and thus boiling temperatures for saturated were not determined. Instead, the temperatures corresponding to the cessation of boiling (i.e., dry out temperatures) of these liquid mixtures were determined. These dry out temperatures range from {approx} 300 C when x(Ca(NO{sub 3}){sub 2}) = 0 to {ge} 400 C when x(Ca(NO{sub 3}){sub 2}) = 0.20 and 0.25. The investigated mixture compositions correspond to some of the major mineral assemblages that are predicted to control the deliquescence relative humidity of salts formed by leaching dust samples from the proposed nuclear repository at Yucca Mountain, Nevada.},
doi = {10.2172/889972},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Nov 29 00:00:00 EST 2005},
month = {Tue Nov 29 00:00:00 EST 2005}
}

Technical Report:

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  • Boiling temperature measurements have been made at ambient pressure for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O, NaNO{sub 3} + KNO{sub 3} + H{sub 2}O, and NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O over the full composition range, along with those of the single salt systems. Boiling temperatures were also measured for the four component NaCl + NaNO{sub 3} + KNO{sub 3} + H{sub 2}O and five component NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O mixtures, where the solute mole fraction of Ca(NO{sub 3}){sub 2}, x(Ca(NO{sub 3}){sub 2}),more » was varied between 0 and 0.25. The maximum boiling temperature found for the NaCl + KNO{sub 3} + H{sub 2}O system is {approx} 134.9 C; for the NaNO{sub 3} + KNO{sub 3} + H{sub 2}O system is {approx} 165.1 C at x(NaNO{sub 3}) {approx} 0.46 and x(KNO{sub 3}) {approx} 0.54; and for the NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O system is 164.7 {+-} 0.6 C at x(NaCl) {approx} 0.25 and x(Ca(NO{sub 3}){sub 2}) {approx} 0.75. The NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O system forms molten salts below their maximum boiling temperatures, and the temperatures corresponding to the cessation of boiling (dry out temperatures) of these liquid mixtures were determined. These dry out temperatures range from {approx} 300 C when x(Ca(NO{sub 3}){sub 2}) = 0 to {ge} 400 C when x(Ca(NO{sub 3}){sub 2}) = 0.20 and 0.25. Mutual deliquescence/efflorescence relative humidity (MDRH/MERH) measurements were also made for the NaNO{sub 3} + KNO{sub 3} and NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture from 120 to 180 C at ambient pressure. The NaNO{sub 3} and NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture has a MDRH of 26.4% at 120 C and 20.0% at 150 C. This salt mixture also absorbs water at 180 C, which is higher than expected from the boiling temperature experiments. The NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture was found to have a MDRH of 25.9% at 120 C and 10.5% at 180 C. The investigated mixture compositions correspond to some of the major mineral assemblages that are predicted to control brine composition due to the deliquescence of salts formed in dust deposited on waste canisters in the proposed nuclear repository at Yucca Mountain, Nevada.« less
  • Boiling temperature measurements have been made for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O and NaNO{sub 3} + KNO{sub 3} + H{sub 2}O over the full solute mole fraction range, along with the limiting binary solutions NaCl + H{sub 2}O, NaNO{sub 3} + H{sub 2}O, and KNO{sub 3} + H{sub 2}O. Boiling temperatures have also been measured for the quaternary NaCl + NaNO{sub 3} + KNO{sub 3} + H{sub 2}O mixtures with KNO{sub 3}:NaNO{sub 3} mole ratios of 1.01 and 1.19, which corresponding to the eutectic ratio and a near-eutectic ratio for the NaNO{sub 3} +more » KNO{sub 3} + H{sub 2}O subsystem. The maximum boiling temperature found for the NaCl + KNO{sub 3} + H{sub 2}O system is 134 C and for the NaNO{sub 3} + KNO{sub 3} + H{sub 2}O system is 160 C, but boiling temperatures as high as 196 C were measured the NaCl + NaNO{sub 3} + KNO{sub 3} + H{sub 2}O system. These mixture compositions correspond to the major mineral assemblages that are predicted to control the deliquescence relative humidity of salts found by leaching dust samples from the proposed nuclear repository at Yucca Mountain, Nevada.« less
  • We conducted reversed deliquescence experiments in saturated NaCl-NaNO{sub 3}-H{sub 2}O, KNO{sub 3}-NaNO{sub 3}-H{sub 2}O, and NaCl-KNO{sub 3}-H{sub 2}O systems from 90 to 120 C as a function of relative humidity and solution composition. NaCl, NaNO{sub 3}, and KNO{sub 3} represent members of dust salt assemblages that are likely to deliquesce and form concentrated brines on high-level radioactive waste package surfaces in a repository environment at Yucca Mountain, NV, USA. Discrepancy between model prediction and experimental code can be as high as 8% for relative humidity and 50% for dissolved ion concentration. The discrepancy is attributed primarily to the use ofmore » 25 C models for Cl-NO{sub 3} and K-NO{sub 3} ion interactions in the current Yucca Mountain Project high-temperature Pitzer model to describe the non-ideal behavior of these highly concentrated solutions.« less
  • The electrolytes Ca(NO{sub 3}){sub 2}(aq) and NaNO{sub 3}(aq) are both extremely soluble but differ in several important respects. Ca(NO{sub 3}){sub 2}(aq) has complex behavior at low ionic strengths and forms several thermodynamically stable and metastable solid phases, whereas NaNO{sub 3}(aq) forms only an anhydrous solid phase. The thermodynamic properties of both have previously been modeled using extended Pitzer ion-interaction models that include higher-order virial terms, in addition to those of the standard Pitzer model. The parameters of the original Pitzer model, however, are often needed for thermodynamic modeling calculations. In this paper we convert the parameters of the extended ion-interactionmore » models for Ca(NO{sub 3}){sub 2}(aq) and NaNO{sub 3}(aq) to the standard Pitzer model using an extension of the methodology previously described by Rard and Wijesinghe [J. Chem. Thermodynamics 35 (2003) 439.473]. In this variant, the exponential coefficient {alpha}{sub 1}{sup P} of Pitzer's model is also optimized to yield the most accurate overall representation of the osmotic coefficients {phi} over the ionic strength and temperature ranges of interest. The optimal values of {alpha}{sub 1}{sup P} = 0.87 kg{sup 1/2} {center_dot} mol{sup -1/2} for Ca(NO{sub 3}){sub 2}(aq) and {alpha}{sub 1}{sup P} = 1.43 kg{sup 1/2} {center_dot} mol{sup -1/2} for NaNO{sub 3}(aq) are smaller than the value {alpha}{sub 1}{sup P} = 2.00 kg{sup 1/2} {center_dot} mol{sup -1/2} normally used for electrolytes of these valence types. In both cases, the accuracy of the osmotic coefficients predicted by the standard Pitzer model was nearly equal to that of the extended Pitzer model up to the solubility limit for T = (298.15 to 423.15) K. This result is consistent with the findings of Rard, Wijesinghe, and Wolery [J. Chem. Eng. Data 49 (2004) 1127-1140] who obtained a substantial improvement in model accuracy for Mg(NO{sub 3}){sub 2}(aq) at T = 298.15 K by optimizing this parameter. The use of a temperature dependent {alpha}{sub 1}{sup P}that is optimal at each temperature did not yield a significant improvement in accuracy over using a constant optimal value. We also investigated the impact of choosing different temperature functions to develop temperature correlations for the Pitzer parameters. Higher-order temperature functions were needed for evaluations with solubility limited maximum ionic strength compared to evaluations performed at constant maximum ionic strength over the temperature range, especially for Ca(NO{sub 3}){sub 2}(aq) because of its more complex thermodynamic behavior. Accurate temperature correlations are presented for both Ca(NO{sub 3}){sub 2}(aq) and NaNO{sub 3}(aq).« less