Dielectric and ultrasonic relaxation of LiSCN and LiClO/sub 4/ in dimethoxymethane

Journal Article · Thu Feb 21 04:00:00 EST 1980 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100441a001· OSTI ID:5279948

Saar, D; Brauner, J; Farber, H; Petrucci, S

Ultrasonic absorption at radio frequencies, complex dielectric permittivities at microwave frequencies, electrical conductances, and infrared spectra of solutions of LiSCN and LiClO/sub 4/ in dimethoxymethane are reported. The conductance data, analyzed in the concentration range 7 X 10/sup 14/ to 10/sup -2/ M, indicate that the major species are neutral pairs of ions although a significant amount of triple ions are present. Band analysis of the ir spectra of solutions with concentrations equal and above 0.05 M reveal the presence of three major species, ion-pairs quadrupoles and chains, the latter with Li/sup +/ bound also to the S-end of the SCN ion. The dielectric spectra indicate that there are three dipolar species present, the solvent and two solute species, in accord with information from the ir spectra. Alternate analysis of the dielectric spectra in terms of a Cole-Davidson distribution does not seem to be consistent with the ir findings. Consequently a possible theoretical interpretation of the Cole-Davidson spectrum (based on our earlier proposed mechanism of collisional diffusion and rotation of ion pairs) is considered as unlikely to be relevant. The same applies to recent improvements on our proposal based on a three-dimensional diffusion model. With the aid of the structural information above, the ultrasonic spectra at c approx. 0.1 M for both LiSCN and LiClO/sub 4/ are interpreted as due to an ion-pair-quadrupole equilibrium involving cation desolvation. At higher concentrations a new relaxation process centered at approx. 10 MHz appears.

• Research Organization: Polytechnic Inst. of New York, Brooklyn
• OSTI ID: 5279948
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 84:4; ISSN JPCHA
• Country of Publication: United States
• Language: English

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