The role of external electric fields in enhancing ion mobility, drift velocity, and drift–diffusion rates in aqueous electrolyte solutions

Abstract

Molecular simulations have been carried out using the method of molecular dynamics to investigate the role of external electric fields on the ion mobility, drift velocity, and drift-diffusion rate of ions in aqueous electrolyte solutions. These properties are critical for a range of processes including electrodialysis, electro-deionization, electrophoresis, and electroosmosis. Our results show that external electric fields relax the hydrated ion structure at significantly larger time scales (between 300 and 800 ps), than most other relaxation processes in solutions (generally of the order of 1 ps). Previous studies that did not account for the much longer relaxation times did not observe this behavior for ions even with very high electric fields. External electric fields must also overcome several (at least two or more) activation energy barriers to significantly change the structure of hydrated ions. As a result, the dynamic behavior changes almost in bands as a function of electric field strengths, rather than linearly. Finally, the effect of the field is much less dramatic on water than the ions. Thus electric fields will be of more significance in processes that involve the transport of ions (such as electro-deionization) than the transport of water (electroosmosis).