Electrochemical Analysis of Attoliter Water Droplets in Organic Solutions through Partitioning Equilibrium

Herein, we report the electrochemical monitoring of attoliters of water droplets in an organic medium by the electrolysis of an extracted redox species from the continuous phase upon collisional events on an ultramicroelectrode. To obtain information about a redox-free water droplet in an organic solvent, redox species with certain concentrations need to be contained inside it. The redox species inside the droplet were delivered by a partitioning equilibrium between the organic phase and the water droplets. The mass transfer of the redox species from the surrounding organic phase to the droplet is very fast because of the radial diffusion, which resultantly establishes the equilibrium. Upon the collisional contact between the droplet and the electrode, the extracted redox species in the water droplets were selectively electrolyzed, even though the redox species in the organic continuous phase remained unreacted because of the different solvent environments. The electrolysis of the redox species in the droplets, where the concentration is determined by the equilibrium constant of the redox species in water/oil, can be used to estimate the size of single water droplets in an organic solution.