Thermodynamic experiments in electrosorption systems yield the Gibbs free energy of adsorption, the formal charge transfer coefficient, the limiting double-layer capacity, the maximum surface concentration, the limiting potential shift of the potential of zero charge by the monolayer of adsorbate, and the attraction interaction constant as a more important result. These data for Bi single-crystal electrodes have been related to the geometrical arrangement of the adsorbate and its microscopic data, e.g. dipole moment values in the gas phase and adsorbed state, the length and molar volume of adsorbate molecule, the number of water molecules replaced by one adsorbed molecule of organic compound. The data has been compiled and discussed for many aliphatic compounds on single-crystal Bi planes, compared with the data for Bi solid drop and Hg electrodes. Small positive values of the formal charge transfer coefficient (0 < y < 0.09) have been obtained characterising the substitution of water clusters, consisting of two or three water molecules, and a small dipole contribution of the functional group of adsorbate, which is directed toward the solution.