Dielectric spectroscopy of aqueous solutions of KCl and CsCl

被引:128
作者
Chen, T
Hefter, G [1 ]
Buchner, R
机构
[1] Murdoch Univ, Chem DSE, Murdoch, WA 6150, Australia
[2] Univ Regensburg, Inst Phys & Theoret Chem, D-93040 Regensburg, Germany
关键词
D O I
10.1021/jp026429p
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
Results of a dielectric relaxation study of the aqueous solutions of KCl and CsCl at 25 degreesC are reported using measurements with a vector network analyzer (0.2 less than or equal to nu/GHz less than or equal to 20) and with waveguide interferometers (27 less than or equal to nu/GHz less than or equal to 89). Similar to previously reported data for NaCl,, the spectra of both salts are well fitted by a Cole-Cole equation, although a double-Debye model is competitive at intermediate CsCl concentrations. The impact of the solute on the water structure, reflected in a decrease in the bulk-water relaxation time with rising electrolyte concentration, decreases in the sequence NaCl > KCl > CsCl and appears to be proportional to the surface-charge density of the cation. The interactions of K+ and Cs+ with their hydration shells are too weak to cause irrotational bonding of H2O molecules. It is argued that CsCl exhibits weak ion pairing, although the data are not sufficiently accurate to determine the extent of association and the nature of the ion pair formed.
引用
收藏
页码:4025 / 4031
页数:7
相关论文
共 52 条
[1]  
[Anonymous], 1991, ACTIVITY COEFFICIENT, DOI DOI 10.1201/9781351069472
[2]  
[Anonymous], 1985, ION SOLVATION
[3]   KINETICS OF ION ASSOCIATION IN MANGANESE SULFATE SOLUTIONS .2. THERMODYNAMICS OF STEPWISE ASSOCIATION IN WATER [J].
ATKINSON, G ;
KOR, SK .
JOURNAL OF PHYSICAL CHEMISTRY, 1967, 71 (03) :673-&
[4]  
Baes C.F., 1976, HYDROLYSIS CATIONS
[5]   DIELECTRIC-RELAXATION OF AQUEOUS-ELECTROLYTE SOLUTIONS .2. ION-PAIR RELAXATION OF 1/2, 2/1, AND 2/2 ELECTROLYTES [J].
BARTHEL, J ;
HETZENAUER, H ;
BUCHNER, R .
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1992, 96 (10) :1424-1432
[6]   A COMPUTER-CONTROLLED SYSTEM OF TRANSMISSION-LINES FOR THE DETERMINATION OF THE COMPLEX PERMITTIVITY OF LOSSY LIQUIDS BETWEEN 8.5-GHZ AND 90-GHZ [J].
BARTHEL, J ;
BACHHUBER, K ;
BUCHNER, R ;
HETZENAUER, H ;
KLEEBAUER, M .
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1991, 95 (08) :853-859
[7]   Dielectric relaxation spectroscopy of electrolyte solutions. Recent developments and prospects [J].
Barthel, J ;
Buchner, R ;
Eberspacher, PN ;
Munsterer, M ;
Stauber, J ;
Wurm, B .
JOURNAL OF MOLECULAR LIQUIDS, 1998, 78 (1-2) :83-109
[8]   ELDAR, A KNOWLEDGE BASE SYSTEM ON MICROCOMPUTER FOR ELECTROLYTE-SOLUTIONS - THE FACTUAL KNOWLEDGE OF ELDAR [J].
BARTHEL, J ;
POPP, H .
JOURNAL OF CHEMICAL INFORMATION AND COMPUTER SCIENCES, 1991, 31 (01) :107-115
[9]  
BARTHEL J, 1979, MOD ASPECT ELECTROC, V13, pCH1
[10]  
BARTHEL J, 1998, PHYSICAL CHEM ELECTR