ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Temperature jump experiments with a characteristic heating time of 0.5 ms are used to study the kinetics of liquid/liquid phase separation in noncritical mixtures of 2,6-dimethyl pyridine and water (||x-xc||〉0.02; x, mole fraction of 2,6-dimethyl pyridine; xc, critical composition) as functions of composition and supersaturation. The response of the system to a temperature jump is monitored by measuring the intensity of light scattered by the sample at different scattering angles aitch-theta (30°〈aitch-theta〈90°) as a function of time (up to several seconds). Starting from a level of constant intensity reached with a time constant in the range of milliseconds after a temperature jump the scattered intensity increases with time. For small supersaturations consecutive maxima and minima of scattered intensity develop.They reflect diffusion limited growth of droplets of the emerging second liquid phase (linear relationship between the square of the radius of growing droplets and time). The growth rate increases with increasing supersaturation. Practically no nucleation barrier is found for the onset of growth of droplets for small supersaturations and compositions (||x−xc||〉0.03). The number density N of growing droplets is obtained from simultaneous measurements of scattered intensity and turbidity. For small supersaturations N is independent of time but changes with supersaturation in a characteristic way (classical nucleation model). There exists an upper limit of overheating δT* above which the number density N increases drastically. The ratio (δT*/ΔTc,p) is independent of the reduced temperature ε˜ of phase separation (ε˜=ΔTc,p/Tc; ΔTc,p=Tc−Tp; Tc, critical temperature, Tp, temperature of phase separation). This is expected for mixtures of noncritical composition. The theory proposed by Langer and Schwartz to treat nucleation and growth of droplets in metastable near critical fluids does not describe the phenomena observed in this study. The composition of the samples used (||x−xc||〉0.02) appears to be too far away from the critical.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.458718
