The specific heat C(p) at constant pressure, the shear viscosity eta(s), and the mutual diffusion coefficient D of the 2,6-dimethylpyridine-water mixture of critical composition have been measured in the homogeneous phase at various temperatures near the lower critical demixing temperature T(c). The amplitude of the fluctuation correlation length xi(0)=(0.198+/-0.004) nm has been derived from a combined evaluation of the eta(s) and D data. This value is in reasonable agreement with the one obtained from the amplitude A(+)=(0.26+/-0.01) J(g K) of the critical term in the specific heat, using the two-scale-factor universality relation. Within the limits of error the relaxation rate Gamma of order parameter fluctuations follows power law with the theoretical universal exponent and with the amplitude Gamma=(25+/-1)x10(9) s(-1). No indications of interferences of the critical fluctuations with other elementary chemical reactions have been found. A noteworthy result is the agreement of the background viscosity eta(b), resulting from the treatment of eta(s) and D data, with the viscosity eta(s)(nu=0) extrapolated from high-frequency viscosity data. The latter have been measured in the frequency range of 5-130 MHz using a novel shear impedance spectrometer.

The nature and origin of sound attenuation due to critical fluctuations near the liquid consolute point are discussed. Starting from basic principles, the background of critical phenomena is reviewed and the conceptions of theoretical approaches to describe the critical contributions to the propagation of sound are analysed. Experimental broadband spectra of suitable binary systems are evaluated jointly with results from quasi-elastic light scattering, shear viscosity and heat capacity measurements to verify or disprove theoretical predictions. It is shown that spectra of systems without or with only small-amplitude ultrasonic contribution from noncritical relaxation processes can be represented by theory with the asymptotic high-frequency sonic attenuation coefficient as a simple adjustable parameter. As a result, sonic spectra of more complex systems, exhibiting significant contributions from noncritical ultrasonic relaxations, are discussed assuming the critical part to be known from theory and auxiliary data. This modus operandi allows for a clear extraction of parameters relevant to the noncritical elementary processes in liquid mixtures, such as conformational changes, protolysis and hydrolysis reactions, monomer exchange from micelles and rotational isomerizations of membrane molecules. The influence of the critical dynamics on the noncritical kinetics is disclosed for some topical examples. Adiabatic couplingconstant 25 4. Mixtures featuring noncritical relaxation phenomena 26 4.1. Elementary reactions 26 4.2. Micelle formation 29 4.3. Membrane domain structure fluctuations and axial diffusion 31 5. Conclusions and perspectives 33 Acknowledgments 34 References 34

At temperatures between 30 degrees C and 58 degrees C we have recorded the heat capacity of the ionic ethylammonium nitrate-n-octanol mixture of critical composition and also of the constituents. Different samples of the binary mixture have been measured with its upper critical demixing temperature T(c) varying between 41.04 degrees C and 46.87 degrees C, depending on small traces of water within the liquid under test. Almost identical heat capacity profiles result if the data are displayed as a function of the temperature distance to the actual T(c) value. In the homogeneous phase the critical contribution exhibits power-law behavior with the critical exponent alpha=0.11 as theoretically predicted for nonionic liquids and in conformity with our understanding of the ionic criticality as being asymptotically Ising like. The noncritical background part of the heat capacity can be related to the heat capacities of the constituents using a simple mixture relation. In the two-phase regime a series of almost perfectly reproducible events is found which may be taken to indicate the existence of nonequilibrium intermediate states in the ethylammonium nitrate-n-octanol system.

Between 200 kHz and 130 MHz, the ultrasonic attenuation spectrum of the ionic ethylammonium nitrate--n-octanol mixture of critical composition has been measured at various reduced temperatures (1.5 x 10(-4)

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Ultrasonic attenuation spectra (30 kHz e ν e 400 MHz) of the isobutyric acid/water mixture of critical composition and also of the acid itself (50 kHz e ν e 1100 MHz) are discussed at different temperatures. Quasielastic light scattering data from photon correlation spectrometry of the critical system are evaluated to yield the amplitude D 0 of the mutual diffusion coefficient in the homogeneous phase. Using literature values for the amplitude of the fluctuation correlation length, the background and critical part of the heat capacity, and the linear coefficient in the pressure dependence of the critical temperature T C , the sonic attenuation spectrum as predicted by the Bhattacharjee-Ferrell model has been calculated for the critical mixture at T C . Following again this theoretical model, the contribution due to concentration fluctuations at the temperatures of measurement and also the high-frequency asymptotic background contribution has been subtracted from the experimental spectra. The resulting excess attenuation spectra of the isobutyric acid/water mixture reveal two relaxation processes, both characterized by a discrete relaxation time. These Debye-type relaxations are discussed in terms of the monomer/linear dimer and linear dimer/cyclic dimer equilibria of the carboxylic acid. The relaxation times of the mixture of critical composition exhibit slowing characteristics in the chemical reactions near the critical temperature (T -T C < 5 K) which cannot be explained by the critical behavior of the viscosity. Rather there seems to be an intrinsic effect that slows down near the critical point.

Acoustical attenuation spectrometry, dynamic light scattering, shear viscosity, density, and heat capacity measurements of the methanol/n-hexane mixture of critical composition have been performed. The critical part in the sonic attenuation coefficients nicely fits to the empirical scaling function of the Bhattacharjee-Ferrell [Phys. Rev. A 24, 1643 (1981)] dynamic scaling model if the theoretically predicted scaled half-attenuation frequency Omega(12) (BF)=2.1 is used. The relaxation rates of order parameter fluctuations, as resulting from the acoustical spectra, within the limits of experimental error agree with those from a combined evaluation of the light scattering and shear viscosity measurements. Both series of data display power law with amplitude Gamma(0)=44x10(9) s(-1). The amplitude of the fluctuation correlation length follows as xi(0)=0.33 nm from the light scattering data and as xi(0)=0.32 nm from the amplitude of the singular part of the heat capacity if the two-scale factor universality relation is used. The adiabatic coupling constant g=0.11 results from the amplitude of the critical contribution to the acoustical spectrum near the critical point, in conformity with g=0.12 as following from the variation of the critical temperature with pressure along the critical line and the thermal expansion coefficient.

Based on a representation of the sound velocity of critical liquids in terms of a frequency-dependent complex specific heat at constant pressure, a simple relation between the low-frequency normalized sonic attenuation coefficient and the correlation length of fluctuations is derived. This relation provides a promising alternative for the determination of the dynamics exponent and thus the critical exponent of the shear viscosity. Sonic attenuation data from the literature, measured at frequencies down to 50 kHz, are re-evaluated with a view of the viscosity exponent determination. It is found that only in a small temperature range, the major requirement of the approach is fulfilled with the available data. Close to the critical temperature, the frequencies of measurement are still insufficiently small as compared to the inverse relaxation time of order parameter fluctuations. Criteria for future experiments are discussed briefly.