Abstract
The rotational correlation time τ 1R of acetylene and of the first members of the 1- n-alkyne series have been determined for solutions in n-heptane by means of infrared and Raman spectroscopy. As expected τ 1R increases in the series. Acetylene however should be considered apart as this molecule rotates more freely than the others. Results are interpreted by means of a hydrodynamic model or by a free-volume model. The latter yields very good agreement with experiment in the case of acetylene. On the contrary the rotation of hexyne can be explained by the hydrodynamic theory in the slip boundary condition. For the other molecules, none of the models yields good agreement with experimental data. They require a model in which collisional and hydrodynamic effects will be included.
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