Arbitrarily slow, non-quasistatic, isothermal transformations

Department of Physics, Simon Fraser University - Burnaby, B.C., V5A 1S6, Canada

Received: 25 March 2016
Accepted: 10 June 2016

Abstract

For an overdamped colloidal particle diffusing in a fluid in a controllable, virtual potential, we show that arbitrarily slow transformations, produced by smooth deformations of a double-well potential, need not be reversible. The arbitrarily slow transformations do need to be fast compared to the barrier crossing time, but that time can be extremely long. We consider two types of cyclic, isothermal transformations of a double-well potential. Both start and end in the same equilibrium state, and both use the same basic operations —but in different order. By measuring the work for finite cycle times and extrapolating to infinite times, we found that one transformation required no work, while the other required a finite amount of work, no matter how slowly it was carried out. The difference traces back to the observation that when time is reversed, the two protocols have different outcomes, when carried out arbitrarily slowly. A recently derived formula relating work production to the relative entropy of forward and backward path probabilities predicts the observed work average.