Diluting the hydrogen bonds in viscous solutions of n-butanol with n-bromobutane: a dielectric study

Glass-forming monohydroxy alcohols exhibit not only a structural relaxation but also a slower, single-exponential Debye-type relaxation process which already freezes in the liquid phase. By using dielectric spectroscopy, we study how these relaxations evolve when the aprotic alkyl halide n-bromobutane is added to n-butanol, thereby diluting the hydrogen-bond network. The structural relaxation times smoothly vary over the concentration range of this completely miscible binary system. The Debye process remains unaffected by the dilution of the OH groups up to n-bromobutane mole fractions of about 50%. For larger hydroxy dilutions, it turns rather abruptly into a feature which develops significant spectral broadening and it becomes faster. In the dilute limit, the decoupling between the time scale of the Debye process and that of the structural relaxation amounts to almost 6 decades when extrapolated to the glass transition temperature. This relatively large, strongly concentration dependent decoupling is interpreted in analogy to normal modes in polymers. The present results suggest that the structural and the Debye-like responses of monohydroxy alcohols are unrelated.