Alcoholic Compounds–Physical Properties and Classification Categories, Including Monohydric, Dihydric, Polyhydric and Carbohydrate Derivatives

The relationships between molar mass (M), density (ρ), relative static permittivity (ε_r), and refractive index ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msubsup><mml:mi>n</mml:mi> <mml:mi>D</mml:mi> <mml:mrow><mml:mn>20</mml:mn></mml:mrow> </mml:msubsup> </mml:mrow> <mml:annotation>$n_{\text{D}}^{20}$</mml:annotation></mml:semantics> </mml:math> ) of alcohol derivatives are investigated. It is important to determine the partial molar concentration of hydroxyl groups (N_OH) and the partial molar concentration of CH bonds (N_CH) and their effect on the physical properties of ε_r and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msubsup><mml:mi>n</mml:mi> <mml:mi>D</mml:mi> <mml:mrow><mml:mn>20</mml:mn></mml:mrow> </mml:msubsup> </mml:mrow> <mml:annotation>$n_{\text{D}}^{20}$</mml:annotation></mml:semantics> </mml:math> with reference to the Clausius-Mossotti and Lorentz-Lorenz relationships. Unlike ε_r, the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msubsup><mml:mi>n</mml:mi> <mml:mi>D</mml:mi> <mml:mrow><mml:mn>20</mml:mn></mml:mrow> </mml:msubsup> </mml:mrow> <mml:annotation>$n_{\text{D}}^{20}$</mml:annotation></mml:semantics> </mml:math> is a crucial physical criterion for the reliability of the approach. Individual correlations of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msubsup><mml:mi>n</mml:mi> <mml:mi>D</mml:mi> <mml:mrow><mml:mn>20</mml:mn></mml:mrow> </mml:msubsup> </mml:mrow> <mml:annotation>$n_{\text{D}}^{20}$</mml:annotation></mml:semantics> </mml:math> with N_CH or N_OH are recognized for mono-, di-, tri-, tetra-, and polyhydric alcohol derivatives and carbohydrates. When the number of OH groups per molecule exceeds four, nonlinear effects come into play, probably due to polarization effects of the OH group network. The <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msubsup><mml:mi>n</mml:mi> <mml:mi>D</mml:mi> <mml:mrow><mml:mn>20</mml:mn></mml:mrow> </mml:msubsup> </mml:mrow> <mml:annotation>$n_{\text{D}}^{20}$</mml:annotation></mml:semantics> </mml:math> of carbohydrates is largely determined by the N_CH value. Relationships of the empirical E_T(30) polarity parameter of polyhydric alcohols, aqueous carbohydrate solutions, solvent mixtures, and polymers ε_r are demonstrated.