Ultrasonic velocity and heat capacity temperature profiles of various lipid mixtures have been recorded with high accuracy. This included mixtures of phophatidylcholines with different chain length as well as phosphatidylcholine mixtures with diacyl glycerides. Following previous studies relating the heat capacity to the isothermal compressibility of lipids close to the chain melting transition, we found that the measured ultrasonic velocities are very similar to those calculated from the heat capacity. This implies that we are able to determine the compressibility changes from the excess heat capacity and the heat capacity changes from ultrasonic velocity measurements. The sound velocity and heat capacity traces are discussed with respect to the phase diagrams of the lipid mixtures.

Complex dielectric spectra of ethylene glycol and of various derivatives as well as of mixtures of water with an ethylene glycol oligomer and with a poly(ethylene glycol) dimethyl ether oligomer have been measured. The spectra can be well represented by a Cole-Cole [Cole and Cole, J. Chem. Phys. 9, 341 (1941)] spectral function. The extrapolated low frequency (static) permittivity of this function has been evaluated to yield the effective dipole orientation correlation factor of the liquids. The relaxation time of the ethylene glycols displays a characteristic dependence upon the ratio of concentrations of hydrogen bond donating and accepting groups, indicating two opposing effects. With increasing availability of hydrogen bonding sites effects of association and also of dynamical destabilization increase. Both effects exist also in the mixture of water with the oligomers. They are discussed in terms of a wait-and-switch model of dipole reorientation in associating liquids. Another feature in the dependence of the dielectric relaxation time of poly(ethylene glycol)/water mixtures upon mixture composition has been tentatively assigned to precritical demixing behavior of the binary liquids in some temperature range.

The densities and sound velocities of mixtures of water with poly(ethylene glycol), poly(ethylene glycol) monomethylether, and poly(ethylene glycol) dimethylether with mean molar weights between 250 and 500 have been measured as a function of mixture composition and temperature between 10 and 40 degrees C. Isentropic compressibilities are derived from the data and are compared to those for the ethylene glycol/water system and for other organic solvent/water mixtures. Relative minima in the mixture volume to ideal volume ratio and in the dependence of the compressibility upon mixture composition are discussed in terms of the conformational variability of the chainlike oligomers, of hydrogen-bonded networks, and of water clusters between the oligomer chains.

Ultrasonic absorption spectra, measured between 0.1 and 2000 MHz, are discussed for a variety of poly(ethylene glycol) monoalkyl ether/water (CiEj=H2O) mixtures. Depending on the temperature, the surfactant concentration, and on the length of the hydrophobic (Ci) as well as the hydrophilic part (Ej) of the surfactant molecules, the spectra reveal a multitude of shapes. The set of spectra, however, can be consistently described considering (i) a relaxation term representing the monomer exchange of the micellar solutions, (ii) another one that reflects the local fluctuations in the surfactant concentration, and, with several systems, (iii) additional terms due to CiEj associations or conformational isomerizations. The parameters of these terms are discussed in the light of relevant models. Evidence is presented for a more general view of a fluctuation controlled monomer exchange mechanism that combines aspects of both theoretical models, the micelle formation/decay kinetics and dynamics of local concentration fluctuations.

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