Fractional Stokes-Einstein-Debye relation and orientational entropy effects in strongly hydrogen-bonded liquid amides.

The impedance spectroscopy studies performed for two strongly hydrogen-bonded liquid amides: N-methylpropionamide (NMP, CH(3)·NH·CO·C(2)H(5)) and N-ethylacetamide (NEA, C(2)H(5)·NH·CO·CH(3)) have shown that the two centers of the peptide linkage, -NH·CO-, active in the C=OH-N hydrogen bonds formation, exhibit quite different sensibilities to the steric screening effects. In contrast to the oxygen atom, a relatively small change (CH(3)- to C(2)H(5)-) in the screening of the hydrogen atom leads to an essential decrease of the degree of the amide self-association. As a consequence, both the static dielectric permittivity and the orientational entropy increment of NEA are essentially lower than those of NMP. However, it was found that the dynamic processes studied are only weakly influenced (in the case of dc conductivity, σ(DC)) or totally not influenced (the dielectric relaxation time, τ(D)) by the different degrees of NMP and NEA self-association. The experiment shows that for both the amides, the logσ(DC) vs. logτ(D) dependence is nonlinear and can be described with the fractional Stokes-Einstein-Debye relation, σ(DC)τ ≅ const, with the exponent s varying from about -0.8 to about -0.6 in the temperature range from 5 °C to 110 °C.