Characterization of heterogeneous interaction in binary mixtures of ethylene glycol oligomer with water, ethyl alcohol and dioxane by dielectric analysis

Abstract

The associating behaviour of the binary mixtures of ethylene glycol oligomer (EGO), i.e. ethylene glycol (EG), diethylene glycol (DEG) and poly(ethylene glycol)s (PEG200, PEG300, PEG400 and PEG600) with water (W), ethyl alcohol (EA) and 1,4-dioxane (DX) over the entire concentration range at 25 °C have been investigated through their accurately measured values of dielectric constant. The static dielectric constant ε o , high frequency limiting dielectric constant ε ∞ , dielectric relaxation strength Δ ε , excess dielectric parameters ε E 0 and ε E ∞ , effective Kirkwood correlation factor g eff and corrective correlation factor g f of EGO–W, EGO–EA and EGO–DX mixtures were determined to obtain qualitative and quantitative information about the complex formation through H-bond in these systems. Most of the evaluated dielectric parameters of EG and DEG in different ‘cosolvents’ have different characteristics as compared to the PEG–cosolvent mixture. The observed linear and non-linear behaviour of Δ ε against EGO monomer unit mole fraction X confirms the variation in the homogeneous structures in their binary mixtures with concentration variation. Appearance of the maximum in ε E 0 against X plots indicates that a complex stable adduct is formed in the EGO–W mixtures at stoichiometric ratio 1:1.7 for lower oligomers but this ratio seems to be 1.7:1 for higher EGO molecules, which confirms that the EGO size and chain flexibility affects the complex formation between EGO and W. In case of EG–EA mixture 1:1 stoichiometric ratio form stable adduct whereas for higher EGO–EA, it is 3:1, at EGO monomer unit level. The complex formation behaviour of DEG–EA has entirely different characteristics when compared to the other studied EGO–EA mixtures. Although, 1,4-dioxane has weak polar behaviour dielectric properties of EG–DX and DEG–DX confirm the formation of stable adducts at the stoichiometric ratio 2:1 of EGO monomer unit mole fraction to the DX. For the higher EGO–DX mixtures, stable adduct forms at the stoichiometric ratio 9:1. Except DEG–EA mixtures, the EGO–W and EGO–EA form the complex with reduction in the effective number of dipoles. In EG–DX mixtures, the heterogeneous species form with a large reduction in the effective number of dipoles, which changes as the effective number of dipoles increases with the increase in monomer repeat units of EGO. Further the net electronic polarization in these binary mixtures increases due to heterogeneous interaction over the entire mixing concentration range.