Enhanced Formation of Solvent-Shared Ion Pairs in Aqueous Calcium Perchlorate Solution toward Saturated Concentration or Deep Supercooling Temperature and Its Effects on the Water Structure

Tu, Shen; Lobanov, Sergey S.; Bai, Jianming; Zhong, Hui; Gregerson, Jason; Rogers, A. Deanne; Ehm, Lars; Parise, John B.

doi:10.1021/acs.jpcb.9b08009

Title: Enhanced Formation of Solvent-Shared Ion Pairs in Aqueous Calcium Perchlorate Solution toward Saturated Concentration or Deep Supercooling Temperature and Its Effects on the Water Structure

Abstract

As a candidate of Martian salts, calcium perchlorate [Ca(ClO₄)₂] has the potential to stabilize liquid water on the Martian surface because of its hygroscopicity and low freezing temperature when forming aqueous solution. These two properties of electrolytes in general have been suggested to result from the specific cation–anion–water interaction (ion pairing) that interrupts the structure of solvent water. To investigate how this concentration-dependent and temperature-dependent ion pairing process in aqueous Ca(ClO₄)₂ solution leads to its high hygroscopic property and the extreme low eutectic temperature, we have conducted two sets of experiments. First, the effects of concentration on aqueous calcium perchlorate from 3 to 7.86 m on ion pairing were investigated using Raman spectroscopy. Deconvolution of the Raman symmetric stretching band (ν₁) of ClO₄^– showed the enhanced formation of solvent-shared ion pairs upon increasing salt concentration at room temperature. We have confirmed that the low tendency of forming contact ion pairs in concentrated solution contributes to the high hygroscopicity of the salt. Second, the near eutectic samples were studied as a function of temperature by both combined differential scanning calorimetry–Raman spectroscopic experiments and in situ X-ray diffraction. The number of solvent-shared ion pairs was found to increase with decreasing temperature whenmore »« less

Authors:

^[1]; Lobanov, Sergey S. ^[2]; Bai, Jianming ^[3]; Zhong, Hui ^[1]; Gregerson, Jason ^[1]; Rogers, A. Deanne ^[1]; Ehm, Lars ^[4]; Parise, John B. ^[4]

Stony Brook Univ., Stony Brook, NY (United States)
Stony Brook Univ., Stony Brook, NY (United States); GFZ German Research Center for Geosciences, Potsdam (Germany)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: 2019-10-22

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1576226

Report Number(s):: BNL-212364-2019-JAAM
Journal ID: ISSN 1520-6106

Grant/Contract Number:: SC0012704

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 123; Journal Issue: 45; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 54 ENVIRONMENTAL SCIENCES

Citation Formats


                    Tu, Shen, Lobanov, Sergey S., Bai, Jianming, Zhong, Hui, Gregerson, Jason, Rogers, A. Deanne, Ehm, Lars, and Parise, John B.. Enhanced Formation of Solvent-Shared Ion Pairs in Aqueous Calcium Perchlorate Solution toward Saturated Concentration or Deep Supercooling Temperature and Its Effects on the Water Structure.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpcb.9b08009.

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                    Tu, Shen, Lobanov, Sergey S., Bai, Jianming, Zhong, Hui, Gregerson, Jason, Rogers, A. Deanne, Ehm, Lars, & Parise, John B.. Enhanced Formation of Solvent-Shared Ion Pairs in Aqueous Calcium Perchlorate Solution toward Saturated Concentration or Deep Supercooling Temperature and Its Effects on the Water Structure.  United States.  https://doi.org/10.1021/acs.jpcb.9b08009

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                    Tu, Shen, Lobanov, Sergey S., Bai, Jianming, Zhong, Hui, Gregerson, Jason, Rogers, A. Deanne, Ehm, Lars, and Parise, John B.. Tue .  
"Enhanced Formation of Solvent-Shared Ion Pairs in Aqueous Calcium Perchlorate Solution toward Saturated Concentration or Deep Supercooling Temperature and Its Effects on the Water Structure".  United States.  https://doi.org/10.1021/acs.jpcb.9b08009.  https://www.osti.gov/servlets/purl/1576226.

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@article{osti_1576226,

  title        = {Enhanced Formation of Solvent-Shared Ion Pairs in Aqueous Calcium Perchlorate Solution toward Saturated Concentration or Deep Supercooling Temperature and Its Effects on the Water Structure},

  author       = {Tu, Shen and Lobanov, Sergey S. and Bai, Jianming and Zhong, Hui and Gregerson, Jason and Rogers, A. Deanne and Ehm, Lars and Parise, John B.},

  abstractNote = {As a candidate of Martian salts, calcium perchlorate [Ca(ClO4)2] has the potential to stabilize liquid water on the Martian surface because of its hygroscopicity and low freezing temperature when forming aqueous solution. These two properties of electrolytes in general have been suggested to result from the specific cation–anion–water interaction (ion pairing) that interrupts the structure of solvent water. To investigate how this concentration-dependent and temperature-dependent ion pairing process in aqueous Ca(ClO4)2 solution leads to its high hygroscopic property and the extreme low eutectic temperature, we have conducted two sets of experiments. First, the effects of concentration on aqueous calcium perchlorate from 3 to 7.86 m on ion pairing were investigated using Raman spectroscopy. Deconvolution of the Raman symmetric stretching band (ν1) of ClO4– showed the enhanced formation of solvent-shared ion pairs upon increasing salt concentration at room temperature. We have confirmed that the low tendency of forming contact ion pairs in concentrated solution contributes to the high hygroscopicity of the salt. Second, the near eutectic samples were studied as a function of temperature by both combined differential scanning calorimetry–Raman spectroscopic experiments and in situ X-ray diffraction. The number of solvent-shared ion pairs was found to increase with decreasing temperature when cooled below the temperature of maximum density of the solution, driven by a change in water toward an ice-like structure in the supercooled regime. The massive presence of solvent-shared ion pairs in turn limits the development of the long-range order in the tetrahedral networks of water molecules, which is responsible for the extremely low eutectic point and deep supercooling effects observed in the Ca(ClO4)2–H2O system.},

  doi          = {10.1021/acs.jpcb.9b08009},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 45,

  volume       = 123,

  place        = {United States},

  year         = {2019},

  month        = {10}

}

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Cited by: 5 works

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Figures / Tables:

Figure 1: (a) Raman spectra of aqueous Ca(ClO₄)₂at different concentrations under room temperature with 3 cm₋₁ resolution compared to that of DI water; (b) an enlarged view of the $ν$₁ band (∼933 cm⁻¹) of ClO₄⁻ with 1 cm⁻¹ resolution; (c) expanding fmhm of the $ν$₁ band with increasing concentrations.more »

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