Fluctuating hydrodynamics of reactive liquid mixtures

Changho Kim, Andy Nonaka, John B. Bell, Alejandro L. Garcia, Aleksandar Donev

Research output: Contribution to journalArticle

Abstract

Fluctuating hydrodynamics (FHD) provides a framework for modeling microscopic fluctuations in a manner consistent with statistical mechanics and nonequilibrium thermodynamics. This paper presents an FHD formulation for isothermal reactive incompressible liquid mixtures with stochastic chemistry. Fluctuating multispecies mass diffusion is formulated using a Maxwell-Stefan description without assuming a dilute solution, and momentum dynamics is described by a stochastic Navier-Stokes equation for the fluid velocity. We consider a thermodynamically consistent generalization for the law of mass action for non-dilute mixtures and use it in the chemical master equation (CME) to model reactions as a Poisson process. The FHD approach provides remarkable computational efficiency over traditional reaction-diffusion master equation methods when the number of reactive molecules is large, while also retaining accuracy even when there are as few as ten reactive molecules per hydrodynamic cell. We present a numerical algorithm to solve the coupled FHD and CME equations and validate it on both equilibrium and nonequilibrium problems. We simulate a diffusively driven gravitational instability in the presence of an acid-base neutralization reaction, starting from a perfectly flat interface. We demonstrate that the coupling between velocity and concentration fluctuations dominates the initial growth of the instability.

Original languageEnglish (US)
Article number084113
JournalJournal of Chemical Physics
Volume149
Issue number8
DOIs
StatePublished - Aug 28 2018

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Hydrodynamics
hydrodynamics
Liquids
liquids
poisson process
reaction-diffusion equations
gravitational instability
nonequilibrium thermodynamics
Molecules
Statistical mechanics
retaining
Computational efficiency
statistical mechanics
Navier-Stokes equation
Navier Stokes equations
molecules
Momentum
Thermodynamics
chemistry
momentum

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Fluctuating hydrodynamics of reactive liquid mixtures. / Kim, Changho; Nonaka, Andy; Bell, John B.; Garcia, Alejandro L.; Donev, Aleksandar.

In: Journal of Chemical Physics, Vol. 149, No. 8, 084113, 28.08.2018.

Research output: Contribution to journalArticle

Kim, Changho ; Nonaka, Andy ; Bell, John B. ; Garcia, Alejandro L. ; Donev, Aleksandar. / Fluctuating hydrodynamics of reactive liquid mixtures. In: Journal of Chemical Physics. 2018 ; Vol. 149, No. 8.
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