Dielectric constants are not the only measure of polarity. Because solvents are used by chemists to carry out chemical reactions or observe chemical and biological phenomena, more specific measures of polarity are required. Most of these measures are sensitive to chemical structure.
The Grunwald–Winstein mY scale measures polarity in terms of solvent influence on buildup of positive charge of a solute during a chemical reaction.
Kosowers Z scale' measures polarity in terms of the influence of the solvent on UV-absorption maxima of a salt, usually pyridinium iodide or the pyridinium zwitterion.
Donor number and donor acceptor scale measures polarity in terms of how a solvent interacts with specific substances, like a strong Lewis acid or a strong Lewis base.
The Hildebrand parameter is the square root of cohesive energy density. It can be used with nonpolar compounds, but cannot accommodate complex chemistry.
Reichardts dye, a solvatochromic dye that changes color in response to polarity, gives a scale of E(30) values. E is the transition energy between the ground state and the lowest excited state in kcal/mol, and (30) identifies the dye. Another, roughly correlated scale (E'(33)) can be defined with Nile red.
The polarity, dipole moment, polarizability and hydrogen bonding of a solvent determines what type of compounds it is able to dissolve and with what other solvents or liquid compounds it is miscible. Generally, polar solvents dissolve polar compounds best and non-polar solvents dissolve non-polar compounds best; hence "like dissolves like". Strongly polar compounds like sugars (e.g. sucrose) or ionic compounds, like inorganic salts (e.g. table salt) dissolve only in very polar solvents like water, while strongly non-polar compounds like oils or waxes dissolve only in very non-polar organic solvents like hexane. Similarly, water and hexane (or vinegar and vegetable oil) are not miscible with each other and will quickly separate into two layers even after being shaken well.
Polarity can be separated to different contributions. For example, the Kamlet-Taft parameters are dipolarity/polarizability (π*), hydrogen-bonding acidity (α) and hydrogen-bonding basicity (β). These can be calculated from the wavelength shifts of 3–6 different solvatochromic dyes in the solvent, usually including Reichardt's dye, nitroaniline and diethylnitroaniline. Another option, Hansen solubility parameters, separates the cohesive energy density into dispersion, polar, and hydrogen bonding contributions.