Abstract

The infrared spectroscopic and thermodynamic properties of H bonding in a number of diol monoalkyl ethers RO(CH2)nOH and RO(CH2)2O(CH2)2OH where R = CH3, C2H5 and C4H9 and n= 2, 3 and 4 are rationalised in terms of their conformational and self-association behaviour in solutions. The half-band width Δtext-decoration:overlineν½ and the apparent integrated absorption intensity B= 1/Cl∫ ln(T0/T)text-decoration:overlineνdtext-decoration:overlineν of the intramoleculary H bonded OH bands and the enthalpy change ΔH° involved in the equilibrium reaction intramolecularly H bonded monomer ⇌ free monomer are linearly correlated with the shift of OH frequency on intramolecular H bonding Δtext-decoration:overlineν(=text-decoration:overlineνfree OH–text-decoration:overlineνH bonded OH). The nature of the self-associated species is found to depend no the stability of gauche conformations of the O(CH2)nO units.

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