High-Speed Schlieren Imaging of Vapor Formation in Electrospray Plume

Previous mechanistic descriptions of electrosprays mostly focused on the dynamics of Taylor cones, initial droplets, and progeny droplets. However, vapor formation during droplet desolvation in an electrospray plume has not been discussed to a great extent. Here, we implement a double-pass on-axis schlieren high-speed imaging system to observe generation and propagation of vapors in an offline electrospray source under different conditions. Switching between turbulent and laminar vapor flow was observed for all of the scanned conditions, which may be attributed to randomly occurring disturbances in the sample flow inside the electrospray emitter. Calculation of mean vapor flow velocity and analysis of vapor flow patterns were performed using in-house developed image processing programs. Experiments performed at different electrospray voltages (0-6 kV), solvent flow rates (100-600 μL min^-1), and methanol concentrations (50-100%), indicate only a weak dependency between electrospray voltage and mean vapor velocity, implying that the vapor is mostly neutral; thus, the vapor is not accelerated by electric field. On the other hand, electrospraying solutions of analytes (with mass 151 Da or 12 kDa) did not remarkably increase the overall vapor flow velocity. The source of vapor's velocity is attributed to the inertia of the electrospray droplets. Although there are some differences between a modern electrospray ionization (ESI) setup and the setup used in our experiment (e.g., using a higher flow rate and larger emitter), we believe the findings of our study can be projected to a modern ESI setup.