Onsager reciprocal relations and chemo-mechanical coupling for chemically-active colloids

TL;DR

This paper investigates the chemo-mechanical coupling in chemically active colloids through Onsager reciprocal relations, demonstrating their validity near equilibrium and breakdown at nonequilibrium steady states, with implications for experimental fluctuations.

Contribution

It provides a detailed analysis of Onsager reciprocal relations for active colloids, including numerical validation and insights into their limitations far from equilibrium.

Findings

Reciprocal relations hold near equilibrium.

Solute advection is crucial for symmetry.

Relations break down at nonequilibrium steady states.

Abstract

Similar to cells, bacteria, and other microorganisms, synthetic chemically-active colloids can harness the energy from their environment through a surface chemical reaction and use its energy to self-propel in fluidic environments. In this paper, we study the chemo-mechanical coupling that leads to the self-propulsion of chemically active colloids. The coupling between chemical reactions and momentum transport is a consequence of the Onsager reciprocal relations. They state that the velocity and the surface reaction rate are related to the mechanical and chemical affinities through a symmetric matrix. A consequence of the Onsager reciprocal relations is that, if a chemical reaction drives the motion of the colloid, then an external force generates a reaction rate. Here, we investigate the Onsager reciprocal relations for a spherical active colloid that catalyzes a reversible surface chemical reaction between two species. We solve the relevant transport equations using a perturbation expansion and numerical simulations to demonstrate the validity of the reciprocal relations around the equilibrium. Our results are consistent with previous studies and highlight the key role of solute advection in preserving the symmetry of the Onsager matrix. Finally, we show that the Onsager reciprocal relations break down around a nonequilibrium steady state, which has implications for the thermal fluctuations of the active colloids used in experiments.