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Title: Low temperature heat capacity and thermodynamic functions of anion bearing sodalites Na 8Al 6Si 6O 24X 2 (X = SO 4, ReO 4, Cl, I)

Abstract

Heat capacities of sulfate, perrhenate, chloride, and iodide sodalites with the ideal formula Na 8Al 6Si 6O 24X 2 (X = SO 4, ReO 4, Cl, I) were measured from 2 K to 300 K using a Quantum Design Physical Property Measurement System (PPMS). From the heat capacity data, the standard thermodynamic functions were determined. All four sodalites undergo a phase transition below room temperature for which thermodynamic parameters were determined. Additionally, the heat capacity of one of the constituent compounds (NaReO 4) was measured.

Authors:
 [1];  [2];  [3];  [2];  [4];  [1];  [2]
  1. Brigham Young Univ., Provo, UT (United States)
  2. Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab.
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Environmental Management (EM)
OSTI Identifier:
1361348
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Thermodynamics
Additional Journal Information:
Journal Volume: 114; Journal ID: ISSN 0021-9614
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Sodalite; Technetium; Rhenium

Citation Formats

Schliesser, Jacob, Lilova, Kristina, Pierce, Eric M., Wu, Lili, Missimer, David M., Woodfield, Brian F., and Navrotsky, Alexandra. Low temperature heat capacity and thermodynamic functions of anion bearing sodalites Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I). United States: N. p., 2017. Web. doi:10.1016/j.jct.2017.05.035.
Schliesser, Jacob, Lilova, Kristina, Pierce, Eric M., Wu, Lili, Missimer, David M., Woodfield, Brian F., & Navrotsky, Alexandra. Low temperature heat capacity and thermodynamic functions of anion bearing sodalites Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I). United States. doi:10.1016/j.jct.2017.05.035.
Schliesser, Jacob, Lilova, Kristina, Pierce, Eric M., Wu, Lili, Missimer, David M., Woodfield, Brian F., and Navrotsky, Alexandra. Thu . "Low temperature heat capacity and thermodynamic functions of anion bearing sodalites Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I)". United States. doi:10.1016/j.jct.2017.05.035.
@article{osti_1361348,
title = {Low temperature heat capacity and thermodynamic functions of anion bearing sodalites Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I)},
author = {Schliesser, Jacob and Lilova, Kristina and Pierce, Eric M. and Wu, Lili and Missimer, David M. and Woodfield, Brian F. and Navrotsky, Alexandra},
abstractNote = {Heat capacities of sulfate, perrhenate, chloride, and iodide sodalites with the ideal formula Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I) were measured from 2 K to 300 K using a Quantum Design Physical Property Measurement System (PPMS). From the heat capacity data, the standard thermodynamic functions were determined. All four sodalites undergo a phase transition below room temperature for which thermodynamic parameters were determined. Additionally, the heat capacity of one of the constituent compounds (NaReO4) was measured.},
doi = {10.1016/j.jct.2017.05.035},
journal = {Journal of Chemical Thermodynamics},
number = ,
volume = 114,
place = {United States},
year = {Thu Jun 01 00:00:00 EDT 2017},
month = {Thu Jun 01 00:00:00 EDT 2017}
}

Journal Article:
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  • Heat capacities of Na{sub 2}SO{sub 4}(aq) solutions have been measured from 140{degree}-300{degree}C at 200 bars using a flow-calorimeter over the molality range of 0.05-1.5 mol{center dot}kg{sup minus 1}. Using the ion-interaction or virial coefficient approach developed by Pitzer (1973, 1979, 1987) and coworkers, and approximating the pressure-dependencies of the various Na{sub 2}SO{sub 4}(aq) thermodynamic quantities with those of NaCl(aq) calculated from the equations of Rogers and Pitzer (1982), the authors measured heat capacities were combined with literature values on heat capacities, enthalpies, and osmotic coefficients at temperatures to 225{degree}C and at pressures mostly at 1 bar or vapor-saturation pressure tomore » yield a comprehensive set of equations for the thermodynamic properties of Na{sub 2}SO{sub 4}(aq) at temperatures 25{degree}-300{degree}C, pressure to at least 200 bars, and molalities to 3.0 mol{center dot}kg{sup minus 1}. Good agreement between experimental and predicted solubilities in water indicate that the ion-interaction model can be used successfully to predict mineral-solution equilibria to 300{degree}C without an explicit accounting for ion-pairs, and demonstrates that heat capacity measurements can be used to obtain reliable high-temperature and high-pressure activity properties of electrolyte solutions. The binary and ternary mixing parameters {theta}{sub ij} and {psi}{sub ijk} are required by the ion-interaction model for calculations for multicomponent mixtures. It was found sufficient to adopt previously determined values for {theta}{sub ij} at 25{degree}C without temperature dependence and, from the solubility data, to determine temperature-dependent {psi}{sub ijk} functions.« less
  • The reaction of Re{sub 2}O{sub 7} with XeF{sub 6} in anhydrous HF provides a convenient route to high-purity ReO{sub 2}F{sub 3}. The fluoride acceptor and Lewis base properties of ReO{sub 2}F{sub 3} have been investigated leading to the formation of [M][ReO{sub 2}F{sub 4}] [M = Li, Na, Cs, N(CH{sub 3}){sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 2}F{sub 3}(CH{sub 3}CN). The ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and Re{sub 3}O{sub 6}F{sub 10{sup {minus}} anions and the ReO{sub 2}F{sub 3}(CH{sub 3}CN) adduct have been characterized in the solidmore » state by Raman spectroscopy, and the structures [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{approximately}3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN have been determined by X-ray crystallography. The structure of ReO{sub 2}F{sub 4}{sup {minus}} consists of a cis-dioxo arrangement of Re-O double bonds in which the Re-F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re{sub 2}O{sub 4}F{sub 7}{sup {minus}} and Re{sub 3}O{sub 6}F{sub 10}{sup {minus}} anions and polymeric ReO{sub 2}F{sub 3} are open chains containing fluorine-bridged ReO{sub 2}F{sub 4} units in which each pair of Re-O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re-F bonds trans to Re-O bonds as in ReO{sub 2}F{sub 4}{sup {minus}} and by the occurrence of both fluorine bridges trans to Re-O bonds. Fluorine-19 NMR spectra show that ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) have cis-dioxo arrangements in CH{sub 3}CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO{sub 2}F{sub 4}{sup {minus}} and ReO{sub 2}F{sub 3}(CH{sub 3}CN), where CH{sub 3}CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN was obtained by hydrolysis of ReO{sub 2}F{sub 3}(CH{sub 3}CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.« less
  • The syntheses and characterization of six monomeric rhenium thiolate complexes and the structural characterization of two useful rhenium starting materials are presented. Pyridine-2-thiol (2), 3,6-bis(dimethyl-tert-butylsilyl)pyridine-2-thiol (3), and pyrimidine-2-thiol (4) were reacted with [Bu{sub 4}N][ReOBr{sub 4}(H{sub 2}O)]{center_dot}2H{sub 2}O (5), [Bu{sub 4}N][ReOBr{sub 4}(OPPh{sub 3})] (6), [ReO{sub 2}(C{sub 5}H{sub 5}N){sub 4}], and [Re(N{sub 2}CO(C{sub 6}H{sub 5}))Cl{sub 2}(PPh{sub 3}){sub 2}] to give [ReO(C{sub 5}H{sub 4}NS){sub 3}] (7), [ReO(C{sub 8}H{sub 12}NSiS){sub 3}] (8), [ReO(OH)(C{sub 11}H{sub 20}NSi{sub 2}S){sub 2}] (9), [Re(N{sub 2}-CO(C{sub 6}H{sub 5}))Cl(PPh{sub 3}){sub 2}(C{sub 5}H{sub 4}NS)] (10), [ReO(C{sub 4}H{sub 3}N{sub 2}S){sub 3}] (11), and [Re(P(C{sub 6}H{sub 5}){sub 3})(C{sub 4}H{sub 3}N{sub 2}S){sub 3}] (12). Crystalmore » structures are reported for the compounds.« less
  • The authors have studied {sup 27}Al NMR spectra of powders of strontium chromate aluminate sodalite (SACr) and calcium tungstate aluminate sodalite (CAW) by the magic angle spinning (MAS) technique and of single-crystal SACr by a static method. They show that the precision in the determination of the quadrupole coupling constant (qcc) from MAS spectra is limited by residual broadening. Both in SACr and in CAW Loewenstein's rule is violated, and the qcc's are among the largest found for Al in a tetrahedral site of an aluminosilicate framework, due to the strong tetragonal distortion that accompanies this violation. MAS spectra inmore » cubic and tetragonal SACr are indistinguishable, compatible with a phase transition mainly due to conformational shearing of the four-membered rings of the framework. In the orthorhombic phases of CAW and SACr, at least four different Al sites can be distinguished: the MAS spectra suggest that the Al sites in the two compounds are very similar. Due to the local character of the NMR information, this does not necessarily imply that they have the same space groups. The empirical relation between {sup 27}Al chemical shifts and bond angles established in (approximately) 1/1 aluminosilicates does not hold for these pure aluminates.« less
  • The extent of coupling of anion vibrations in sodalite is revealed through an examination of the far-infrared spectroscopy of a series of cation- and anion-exchanged isomorphs. Two cation and two anion absorptions in the far-IR are observed, consistent with the predictions of a complete unit cell analysis. While the cation translational frequencies are essentially unperturbed on varying the anion, absorptions of the anion translations are dependent on the cation. The intra-..beta..-cage thermal decomposition of perchloratosodalite into the chlorosodalite supports the assignment of cation and anion far-IR absorptions.