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Accurate Determination of Ion Polarizabilities in Aqueous Solutions

Li, Minglun and Zhuang, Bilin and Lu, Yuyuan and Wang, Zhen-Gang and An, Lijia (2017) Accurate Determination of Ion Polarizabilities in Aqueous Solutions. Journal of Physical Chemistry B, 121 (26). pp. 6416-6424. ISSN 1520-6106. doi:10.1021/acs.jpcb.7b04111.

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[img] PDF (Relationship between polarizability α25DE and concentration csalt (mol/L) for KF, NaCl, NaNO3, CaCl2, Li2SO4, and MgSO4 and the relationship between volume ratio Vss/Vs and salt mole fraction xsalt for KF, NaCl, NaNO3, CaCl2, Li2SO4, and MgSO4 at 25 °C) - Supplemental Material
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We present a novel method for obtaining salt polarizabilities in aqueous solutions based on our recent theory for the refractive index of salt solutions, which predicts a linear relationship between the refractive index and the salt concentration at low concentrations, with a slope determined by the intrinsic values of the salt polarizability and the density of the solution. Here we apply this theory to determine the polarizabilities of 32 strong electrolyte salts in aqueous solutions from refractive index and density measurements. Setting Li^+ as the standard ion, we then determine the polarizabilities of seven cations (Na^+, K^+, Rb^+, Cs^+, Ca^(2+), Ba^(2+), and Sr^(2+)) and seven anions (F^–, Cl^–, Br^–, I^–, ClO_4^–, NO_3^–, and SO_4^(2–)), which can be used as important reference data. We investigate the effect of temperature on salt polarizabilities, which decreases slightly with increasing temperature. The ion polarizability is found to be proportional to the cube of bare ionic radius (r_(bare)^3) for univalent ions, but the relationship does not hold for multivalent ions. Contrary to findings of Krishnamurti, we find no significant linear relationship between ion polarizability and the square of the atomic number (N^2) for smaller ions.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Zhuang, Bilin0000-0003-2934-4264
Lu, Yuyuan0000-0002-4073-678X
Wang, Zhen-Gang0000-0002-3361-6114
Additional Information:© 2017 American Chemical Society. Received: May 1, 2017; Revised: June 7, 2017; Published: June 8, 2017. This work was supported by the National Natural Science Foundation of China (Grant Nos. 21674113 and 21334007) and the International Partnership Program of CAS (Grant No. 121522KYSB20160015). Y.L. acknowledges the Youth Innovation Promotion Association of CAS (Grant No. 2016204) for financial support. B.Z. acknowledges the A-STAR fellowship for financial support. The authors declare no competing financial interest.
Funding AgencyGrant Number
National Natural Science Foundation of China21674113
National Natural Science Foundation of China21334007
Chinese Academy of Sciences121522KYSB20160015
Chinese Academy of Sciences2016204
Agency for Science, Technology and Research (A*STAR)UNSPECIFIED
Issue or Number:26
Record Number:CaltechAUTHORS:20170612-155734285
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Official Citation:Accurate Determination of Ion Polarizabilities in Aqueous Solutions Minglun Li, Bilin Zhuang, Yuyuan Lu, Zhen-Gang Wang, and Lijia An The Journal of Physical Chemistry B 2017 121 (26), 6416-6424 DOI: 10.1021/acs.jpcb.7b04111
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78130
Deposited By: Tony Diaz
Deposited On:12 Jun 2017 23:12
Last Modified:15 Nov 2021 17:37

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