The binary system triethylamine-water near its critical consolute point: An ultrasonic spectrometry, dynamic light scattering, and shear viscosity study

Abstract

Ultrasonic attenuation spectra between 100 kHz and 500 MHz, mutual diffusion coefficients and shear viscosities of the triethylamine/water mixture of critical composition have been measured at various temperatures near the critical one. The broadband ultrasonic spectra reveal two relaxation terms with discrete relaxation time and a term that is subject to a broad relaxation time distribution. The former have been discussed to be due to a protolysis reaction and a structural isomerization. The latter term has been evaluated in the light of the Bhattacharjee–Ferrell dynamic scaling theory, relating the sonic spectrum to fluctuations in the local mixture concentrations. The relaxation rate of the Bhattacharjee–Ferrell term follows power law behavior. However, its amplitude (Γ0=45×109 s−1) is considerably smaller than that derived from the dynamic light scattering and shear viscosity measurements (Γ0=96×109 s−1). This result is assumed to be due to a shear viscosity relaxation. Using density and heat capacity measurements from the literature, the adiabatic coupling constant g of the triethylamine/water system has been derived from the amplitude of the Bhattacharjee–Ferrell term in the ultrasonic spectra and from a thermodynamic relation as well. Again, a discrepancy is found. The ultrasonic spectra yield g=0.19, whereas g=0.98 follows otherwise. This difference in the g values is taken as an indication of the limitations of the Bhattacharjee–Ferrell model. It had been derived assuming a small amplitude in the singular part of the heat capacity, a precondition which is clearly not fulfilled with the triethylamine/water system.