Supersaturation Limit for Homogeneous Nucleation of Oxygen Bubbles in Water at Elevated Pressure: "Super-Henry's Law"

Abstract

At 25 "C and atmospheric pressure, the iodide-catalyzed decomposition of aqueous hydrogen peroxide in an undisturbed solution results in a maximum dissolved oxygen concentration of 0.12 M, or about 100 times the equilibrium solubility. At this concentration loss of gas occurs by homogeneous nucleation of bubbles. The supersaturation is readily destroyed by agitation or by sonication. As the external pressure is increased, the maximum attainable oxygen concentration increases linearly, reaching 0.18 M at 50 atm. In a plot of dissolved gas concentration versus external pressure, the supersaturation line is parallel to the Henry's law (saturation) line. The maximum supersaturation concentration at elevated pressure is independent of the nature of the pressurizing gas. While the pressure dependence of the supersaturation limit can be understood in terms of existing nucleation theory, the theory fails in attempts to calculate that limit quantitatively.

Iodine oxidation by hydrogen peroxide and Bray–Liebhafsky oscillating reaction: effect of the temperature

“…32 The measured k L A/V values depend on many hydrodynamic parameters and values of k L A/V between 0.008 and 0.06 s À1 have been reported in vigorously stirred tank reactors. 34 Other reported values are lower 33 and these studies suggest that, under our experimental conditions, k 12 is not larger than 0.01 s À1 at 251 and does not increase significantly with the temperature. 35 It must also be noted that our simulations of the effect of oxygen on the BL oscillations depend on the empirical parameter k 11 so that a too low (high) value of k 12 , giving a too high (low) value of [O 2 ], can be compensated by a lower (higher) value of k 11 .…”

Synthesis of quantum-confined CdS nanotubes

“…The energy required to form a critical bubble homogeneously (Landau and Lifshitz 1999; Bowers et al 1995) is given by…”

Solubility of gas in confined systems. Nonextensive thermodynamics approach

“…An illustration of this behavior is given in the paper of Bowers et al [40] which shows a "super-Henry's Law" for the solubility of oxygen produced by the catalyzed decomposition of iodine by hydrogen peroxide. In this study, the plot of the concentration of dissolved gas according to the pressure is parallel to the Henry's Law, since it corresponds to the following…”

“…In the work of Bowers et al [31,40], this behavior is considered as particular case of the classical nucleation theory (CNT), for which the rate of nucleation is constant.…”