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A small, bimetallic particle in a hydrogen peroxide solution can propel itself by means of an electrocatalytic reaction. The swimming is driven by a flux of ions around the particle. We model this process for the presence of a monovalent salt, where reaction-driven proton currents induce salt ion currents. A theory for thin diffuse layers is employed, which yields nonlinear, coupled transport equations. The boundary conditions include a compact Stern layer of adsorbed ions. Electrochemical processes on the particle surface are modeled with a first order reaction of the Butler-Volmer type. The equations are solved numerically for the swimming speed. An analytical approximation is derived under the assumption that the decomposition of hydrogen peroxide occurs mainly without inducing an electric current. We find that the swimming speed increases linearly with hydrogen peroxide concentration for small concentrations. The influence of ion diffusion on the reaction rate can lead to a concave shape of the function of speed vs. hydrogen peroxide concentration. The compact layer of ions on the particle diminishes the reaction rate and consequently reduces the speed. Our results are consistent with published experimental data.
Active diffusiophoresis - swimming through interaction with a self-generated, neutral, solute gradient - is a paradigm for autonomous motion at the micrometer scale. We study this propulsion mechanism within a linear response theory. Firstly, we cons ider several aspects relating to the dynamics of the swimming particle. We extend established analytical formulae to describe small swimmers, which interact with their environment on a finite lengthscale. Solute convection is also taken into account. Modeling of the chemical reaction reveals a coupling between the angular distribution of reactivity on the swimmer and the concentration field. This effect, which we term reaction induced concentration distortion, strongly influences the particle speed. Building on these insights, we employ irreversible, linear thermodynamics to formulate an energy balance. This approach highlights the importance of solute convection for a consistent treatment of the energetics. The efficiency of swimming is calculated numerically and approximated analytically. Finally, we define an efficiency of transport for swimmers which are moving in random directions. It is shown that this efficiency scales as the inverse of the macroscopic distance over which transport is to occur.
Surface interactions provide a class of mechanisms which can be employed for propulsion of micro- and nanometer sized particles. We investigate the related efficiency of externally and self-propelled swimmers. A general scaling relation is derived sh owing that only swimmers whose size is comparable to, or smaller than, the interaction range can have appreciable efficiency. An upper bound for efficiency at maximum power is 1/2. Numerical calculations for the case of diffusiophoresis are found to be in good agreement with analytical expressions for the efficiency.
In a spatially periodic temperature profile, directed transport of an overdamped Brownian particle can be induced along a periodic potential. With a load force applied to the particle, this setup can perform as a heat engine. For a given load, the op timal potential maximizes the current and thus the power output of the heat engine. We calculate the optimal potential for different temperature profiles and show that in the limit of a periodic piecewise constant temperature profile alternating between two temperatures, the optimal potential leads to a divergent current. This divergence, being an effect of both the overdamped limit and the infinite temperature gradient at the interface, would be cut off in any real experiment.
Molecular motors transduce chemical energy obtained from hydrolizing ATP into mechanical work exerted against an external force. We calculate their efficiency at maximum power output for two simple generic models and show that the qualitative behavio ur depends crucially on the position of the transition state. Specifically, we find a transition state near the initial state (sometimes characterized as a power stroke) to be most favorable with respect to both high power output and high efficiency at maximum power. In this regime, driving the motor further out of equilibrium by applying higher chemical potential differences can even, counter-intuitively, increase the efficiency.
139 - Tim Schmiedl , Udo Seifert 2007
We study a class of cyclic Brownian heat engines in the framework of finite-time thermodynamics. For infinitely long cycle times, the engine works at the Carnot efficiency limit producing, however, zero power. For the efficiency at maximum power, we find a universal expression, different from the endoreversible Curzon-Ahlborn efficiency. Our results are illustrated with a simple one-dimensional engine working in and with a time-dependent harmonic potential.
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