Hydrogen Bonding in Liquid Water and in the Hydration Shell of Salts

被引:22
作者
Dagade, Dilip H. [1 ]
Barge, Seema S. [1 ]
机构
[1] Shivaji Univ, Dept Chem, Kolhapur 416004, Maharashtra, India
关键词
hydrogen bonds; IR spectroscopy; salt effect; thermodynamics; water chemistry; ENTHALPY-ENTROPY COMPENSATION; NEAR-INFRARED SPECTROSCOPY; KIRKWOOD-BUFF THEORIES; AQUEOUS-SOLUTIONS; 298.15; K; IONIC LIQUIDS; INTERMOLECULAR INTERACTIONS; VIBRATIONAL SPECTROSCOPY; MCMILLAN-MAYER; CCL4; SOLUTIONS;
D O I
10.1002/cphc.201500921
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A near-IR spectral study on pure water and aqueous salt solutions is used to investigate stoichiometric concentrations of different types of hydrogen-bonded water species in liquid water and in water comprising the hydration shell of salts. Analysis of the thermodynamics of hydrogen-bond formation signifies that hydrogen-bond making and breaking processes are dominated by enthalpy with non-negligible heat capacity effects, as revealed by the temperature dependence of standard molar enthalpies of hydrogen-bond formation and from analysis of the linear enthalpy-entropy compensation effects. A generalized method is proposed for the simultaneous calculation of the spectrum of water in the hydration shell and hydration number of solutes. Resolved spectra of water in the hydration shell of different salts clearly differentiate hydrogen bonding of water in the hydration shell around cations and anions. A comparison of resolved liquid water spectra and resolved hydration-shell spectra of ions highlights that the ordering of absorption frequencies of different kinds of hydrogen-bonded water species is also preserved in the bound state with significant changes in band position, band width, and band intensity because of the polarization of water molecules in the vicinity of ions.
引用
收藏
页码:902 / 912
页数:11
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