Understanding Refractive Index Changes in Homologous Series of Unbranched Organic Compounds Based on Beer's Law

Changes of the refractive index for homologous series of hydrocarbons are usually plotted versus the density. While there is a clear linear dependence for alkanes and alkenes, the linearity deteriorates for homologous series with functional groups involving heteroatoms. The slope can even become negative, e. g., for carboxylic acids. For gaining a deeper understanding and to establish a more general correlation, we reinvestigate the corresponding theories starting with the Newton-Laplace, Gladstone-Dale and the Lorentz-Lorenz rules. We revisit the concept of molar refractivity pioneered by Landolt and Brühl and show that it is closely connected with a twin of Beer's law. We conclude that the refractive index of homologues series should better be plotted versus the molar concentration of the main UV-chromophore, the C-H bond, which actually causes the refractive index changes. This new approach is not limited to alkanes and alkenes but holds for homologous series with functional groups including heteroatoms.