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Title: Thermochemical Measurements of Alkali Cation Association to Hexatantalate

Abstract

Ion association is an important process in aqueous dissolution, precipitation, and crystallization of ionic inorganic, organic, and biological materials. Polyoxometalates (POMs) are good model compounds for understanding the complex relationships between lattice energy, ion-pairing in solution, and salt solubility. Here we perform calorimetric measurements to elucidate trends in cluster stability, lattice energy, and ion-pairing behavior studies of simple hexatantalate salts in neat water, parent hydroxide solutions, and molybdate melts, extending previous studies on the isostructural hexaniobates. High temperature calorimetry of alkali salts of hexatantalate reveals that the enthalpies of formation from oxides of the K, Rb, and Cs salts are more similar to each other than they are for their niobate analogues and that the tantalate cluster is energetically less stable than hexaniobate. Aqueous dissolution calorimetry reveals that the cesium salt of hexatantalate has a similar concentration dependence on its dissolution enthalpy to that of hexaniobate. However, unlike rubidium hexaniobate, rubidium hexatantalate also exhibits increased concentration dependence, indicating that hextantalate can undergo increased ion-pairing with alkali salts other than cesium, despite the dilute environments studied. Dissolution enthalpies of POM salts in the parent alkali hydroxides shows that protonation of clusters stabilizes lattices even more than the strongly associating heavy alkalimore » cations do. Additionally, neither weak nor strong lattice ion associations necessarily correlates with respectively high or low aqueous solubility. These studies illuminate the importance of considering ion-pairing among the interrelated processes in the aqueous dissolution of ionic salts that can be extended to serving as a model of cation association to metal oxide surfaces.« less

Authors:
; ; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1472212
Grant/Contract Number:  
SC0010802; FG02‐97ER14749
Resource Type:
Published Article
Journal Name:
Molecules
Additional Journal Information:
Journal Name: Molecules Journal Volume: 23 Journal Issue: 10; Journal ID: ISSN 1420-3049
Publisher:
MDPI AG
Country of Publication:
Switzerland
Language:
English

Citation Formats

Sures, Dylan, Nagabhushana, G., Navrotsky, Alexandra, and Nyman, May. Thermochemical Measurements of Alkali Cation Association to Hexatantalate. Switzerland: N. p., 2018. Web. doi:10.3390/molecules23102441.
Sures, Dylan, Nagabhushana, G., Navrotsky, Alexandra, & Nyman, May. Thermochemical Measurements of Alkali Cation Association to Hexatantalate. Switzerland. doi:10.3390/molecules23102441.
Sures, Dylan, Nagabhushana, G., Navrotsky, Alexandra, and Nyman, May. Mon . "Thermochemical Measurements of Alkali Cation Association to Hexatantalate". Switzerland. doi:10.3390/molecules23102441.
@article{osti_1472212,
title = {Thermochemical Measurements of Alkali Cation Association to Hexatantalate},
author = {Sures, Dylan and Nagabhushana, G. and Navrotsky, Alexandra and Nyman, May},
abstractNote = {Ion association is an important process in aqueous dissolution, precipitation, and crystallization of ionic inorganic, organic, and biological materials. Polyoxometalates (POMs) are good model compounds for understanding the complex relationships between lattice energy, ion-pairing in solution, and salt solubility. Here we perform calorimetric measurements to elucidate trends in cluster stability, lattice energy, and ion-pairing behavior studies of simple hexatantalate salts in neat water, parent hydroxide solutions, and molybdate melts, extending previous studies on the isostructural hexaniobates. High temperature calorimetry of alkali salts of hexatantalate reveals that the enthalpies of formation from oxides of the K, Rb, and Cs salts are more similar to each other than they are for their niobate analogues and that the tantalate cluster is energetically less stable than hexaniobate. Aqueous dissolution calorimetry reveals that the cesium salt of hexatantalate has a similar concentration dependence on its dissolution enthalpy to that of hexaniobate. However, unlike rubidium hexaniobate, rubidium hexatantalate also exhibits increased concentration dependence, indicating that hextantalate can undergo increased ion-pairing with alkali salts other than cesium, despite the dilute environments studied. Dissolution enthalpies of POM salts in the parent alkali hydroxides shows that protonation of clusters stabilizes lattices even more than the strongly associating heavy alkali cations do. Additionally, neither weak nor strong lattice ion associations necessarily correlates with respectively high or low aqueous solubility. These studies illuminate the importance of considering ion-pairing among the interrelated processes in the aqueous dissolution of ionic salts that can be extended to serving as a model of cation association to metal oxide surfaces.},
doi = {10.3390/molecules23102441},
journal = {Molecules},
number = 10,
volume = 23,
place = {Switzerland},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.3390/molecules23102441

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