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Abstract Spreading and mixing are complementary processes that promote reaction of two reactive aqueous solutes present in contiguous plumes in groundwater. Spreading reconfigures the plume geometry, elongating the interface between the plumes, while mixing increases the volume of aquifer occupied by each plume, bringing the solute molecules together to react. Since reaction only occurs where the two solute plumes are in contact with each other, local mechanisms that drive flow and transport near the interface between the plumes control the amount of reaction. This work uses local characteristics of the plumes and the flow field near the plume interface to analyze the relative contributions of pore‐scale mixing and mechanical dispersion to instantaneous, irreversible, bimolecular reaction in a homogeneous aquifer with active spreading caused by radial flow from a well. Two solutes are introduced in sequence at the well, creating concentric circular plumes. We allow for incomplete mixing of the solutes in the pore space, by modeling the pore space as a segregated compartment and a mixed compartment with first‐order mass transfer between the two compartments. We develop semi‐analytical expressions for concentrations of the solutes in both compartments. We found that the relative contribution of mechanical dispersion to reaction increases over time and also increases due to increases in the Peclet number, in the relative source concentration of the chasing solute, and in the mass transfer rate from the segregated compartment to the mixed compartment of the pore space.
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An entropic theory of homogeneous ice nucleation in non-ionic aqueous solutions
The nucleation of ice from aqueous solutions is a process essential to myriad environmental and industrial processes, but the physical factors affecting the capacity of different solutes to depress the homogeneous nucleation temperature of ice are yet poorly understood. In this work, we demonstrate that for many binary aqueous solutions of non-ionic solutes, this depression is dominated by the entropy of the liquid phase. Employing the classic Turnbull interpretation of the interfacial free energy γ∼TSliquid−Ssolid and estimating solution entropies with a Flory-style modification of the ideal entropy of mixing that accounts for solute size effects, we demonstrate that mixing entropy alone predicts experimental homogeneous nucleation temperatures across a wide variety of non-ionic solutions. We anticipate that this physical insight will not only enhance a fundamental understanding of homogeneous nucleation processes across fields but also open new avenues to the rational design of aqueous solutions for desired nucleation behaviors.
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- Award ID(s):
- 1941543
- PAR ID:
- 10593858
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 160
- Issue:
- 10
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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