Homogeneous nucleation of liquid from the vapor phase in an expansion cloud chamber

A Wilson expansion cloud chamber has been used to measure the homogeneous vapor-to-liquid nucleation of several materials over the past decade. These data, representing nucleation rate as a function of temperature and supersaturation ratio for toluene, nonane, and water measured in our center, have been re-examined and are presented both in graphical form and as a table of selected data points. The latter is included for ease of comparison with theory. Measurements of the binary homogeneous nucleation of ethanol-water (E-W) mixtures are also presented. The expansion chamber experimental technique and data reduction technique are discussed

Scaling of Nucleation Rates

The homogeneous nucleation rate, J, for T ≪ Tc can be cast into a corresponding states form by exploiting scaled expressions for the vapor pressure and for the surface tension, σ. In the vapor-to-liquid case with σ = σ0[Tc-T], the classical cluster energy of formation /kT = [16π/3]·Ω3[Tc/T-1]3/(ln S)2 ≡ [x0/x]2, where Ω ≡ σ0[k ñ2/3] and ñ is liquid number density. The Ω ≈ 2 for normal liquids. (A similar approach can be applied to homogeneous liquid to solid nucleation and to heterogeneous nucleation formalisms using appropriate modifications of σ and Ω.) The above [x0/x]2 is sufficiently tenable that in some cases, one can use it to extract approximate critical temperatures from experimental data. In this work, we point out that expansion cloud chamber data (for nonane, toluene, and water) are in excellent agreement with ln J ≈ const. - [x0/x]2 [centimeter-gram-second (cgs) units], and that the constant term is well approximated by ln (Γc), where Γc is the inverse thermal wavelength cubed per second at T = Tc. The ln (Γc) is ≈ 60 in cgs units (74 in SI units) for most materials. A physical basis for the latter form, which includes the behavior at small n, the discrete integer behavior of n, and a configurational entropy term, τ ln (n), is presented