Non-equilibrium state during proton-deuteron exchange at a liquid-liquid interface
Tillmann Buttersack, Niclas Sven Mueller, Giulia Carini, Henrik Haak, Hanna Bordyuh, Dipali Singh, Sandy Gewinner, Marco De Pas, Wieland Schöllkopf, Martin Wolf, Hendrik Bluhm, Nils Huse, Bernd Winter, Gerard Meijer, Alexander Paarmann
Published: 2025/9/22
Abstract
The exchange of protons and deuterons is a very fast process, even on macroscopic length scales. Here we directly measure quantitatively the formation of HDO within the first 100 microseconds of the reaction at the liquid-liquid interface between D$_2$O and H$_2$O using a fast-flowing liquid flat jet and infrared spectroscopic imaging. During early stages of the reaction, the rate of HDO formation is limited by the availability of hydroxide and hydronium ions mediating the reaction, rather than simply by diffusion. This reveals a non-equilibrium state of the interface, being fully mixed diffusely yet with HDO concentrations well below equilibrium. We extract the reaction rate constant for the HDO formation in good agreement with picosecond timescales of the elementary proton-deuteron exchange reaction. Quantitative analysis of educt and product concentrations by infrared imaging at well-defined liquid-liquid interfaces as introduced here will enable studying fast kinetics for a wide range of chemical reactions.