A fist-principles nonlocal pseudopotential is applied to study the thermodynamic excess entropy of mixing and the electrical resistivity of Na-based liquid binary alloys. We show that both these properties can be studied simultaneously and self-consistently. For the two Na-based liquid alloys, the results obtained for the excess entropies of mixing are compared with each other in order to see the importance of various contributions and their physical signifkances. When compared with experimental data, we find that the input densities to the present calculation are crucial and must be highly reliable if an accurate excess entropy of mixing is to be obtained. The same input sources are then used to calculate the electrical resistivity for the Na-Pb system. It appears that the partial localisation of valence electrons on the more electronegative ions is the cause for the anomalies found in this liquid alloy system.