We have studied the structure of a monolayer of C21H 43OH on water, in the region near close packing, by grazing incidence in-plane x-ray diffraction. For all temperatures studied the isotherms in the πa plane show a kink, signaling a phase transition. Along an isotherm, and for pressures above the kink, we observe that the transverse structure factor has one peak which has constant position, width, and intensity; below the kink the diffraction peak shifts to smaller scattering vector (larger separation) and the amplitude decays as the surface pressure decreases, but the width of the peak remains constant. We rationalize these observations in terms of the influence on the transverse structure factor of gauche configurations in the amphiphile tails, with the kink representing the point at which the last of the gauche configurations is squeezed out of the chain. Along an isobar which is at higher pressure than the kink pressures of all isotherms crossed, the transverse structure factor has a single peak above a transition temperature and two peaks below that temperature; for π = 30 dyn/cm the transition temperature is in the range 16.3 < T < 21.3°C. We interpret this observation, by comparison with the properties of the lamellar crystalline n-paraffins, as a hexagonal-to-pseudohexagonal structural transition analogous to the crystal rotator II-to-rotator I transition. Our results imply that the hydrocarbon tails of the amphiphile molecules dominate the properties of the monolayer.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry