Vibrational spectroscopic studies of aqueous solutions of tert-butyl alcohol and tert-butylamine

Raman and FT-IR absorption spectra of aqueous tert-butyl alcohol (t-BuOH) and tert-butylamine (t-BuNH2) in the region of the O–H and NH2 stretching and bending modes have been measured as a function of organic co-solvent concentration in the whole co-solvent mole fraction region. The major observed changes of the aqueous binary solution spectra compared with the solvent spectra are a loss or gain of band intensity. In particular, the observed changes in intensities and linewidths of some bands were significantly more pronounced at low concentrations of organic co-solvents in water, where t-BuOH and t-BuNH2 tend to integrate into the water structure. Clear evidence of structural enhancement of the network is obtained in dilute solutions as well as destruction of the network by hydrophobic interactions as the concentration is increased. Generally, the interpretation of the spectra is in agreement with the capacity of the hydrophobic co-solvent to break the structure of water in the more concentrated aqueous solutions and to enhance the structure in dilute solutions. Vibrational intensities and frequency shifts of some bands show definite trends with varying the concentration of the solutions. In the concentration-dependence study, unusual linewidth changes of certain bands were observed.Key words: infrared, Raman spectra, aqueous, tert-butanol, tert-butylamine.