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Infra-red spectra are reported of complexes of 2,2,2-trifluoroethanol with a wide range of proton donors, and of alkanols with several ethers, in the vapour phase in a 1 m path-length cell. Equilibrium constants at different temperatures and the enthalpy of association of the complex are derived for the trifluoroethanol-tetrahydrofuran, propene oxide and ethene oxide, and the 2methylpropan-2-ol-ethene oxide systems.