Chemical Physics Letters, Vol.384, No.4-6, 224-228, 2004
Rapidly fluctuating ion complexes in aqueous solutions of 2 : 1 valent salts
Ultrasonic absorption spectra at frequencies between 300 kHz and 3 GHz are reported for aqueous solutions of MgCl2 CaCl2, SrCl2, NiCl2, and CuCl2. All spectra reveal a Debye-type relaxation term with small amplitude. The relaxation time values derived from the spectra display a small range only (0.2 ns less than or equal to tau less than or equal to 0.6 ns), corresponding with the tau values for solutions of Mg(NO3)(2) and Ca(NO3)(2) in water. The relaxation term is suggested to be due to the second step in the Eigen-Tamm scheme of stepwise association and dissociation of ions, namely the equilibrium between the complex of encounter and the outer sphere complex. The relaxation amplitudes reflect special properties of the ions. (C) 2003 Elsevier B.V. All rights reserved.