Exploring Gas–Liquid Reactions with Microjets: Lessons We Are Learning

Abstract

Conspectus Liquid water is all around us: at the beach, in a cloud, from a faucet, inside a spray tower, covering our lungs. It is fascinating to imagine what happens to a reactive gas molecule as it approaches the surface of water in these examples. Some incoming molecules may first be deflected away after colliding with an evaporating water molecule. Those that do strike surface H2O or other surface species may bounce directly off or become momentarily trapped through hydrogen bonding or other attractive forces. The adsorbed gas molecule can then desorb immediately or instead dissolve, passing through the interfacial region and into the bulk, perhaps diffusing back to the surface and evaporating before reacting. Alternatively, it may react with solute or water molecules in the interfacial or bulk regions, and a reaction intermediate or the final product may then desorb into the gas phase. Building a “blow by blow” picture of these pathways is challenging for vacuum-based techniques because of the high vapor pressure of water. In particular, collisions within the thick vapor cloud created by evaporating molecules just above the surface scramble the trajectories and internal states of the gaseous target molecules, hindering construction of gas–liquid reaction mechanisms at the atomic scale that we strive to map out. The introduction of the microjet in 1988 by Faubel, Schlemmer, and Toennies opened up entirely new possibilities. Their inspired solution seems so simple: narrow the end of a glass tube to a diameter smaller than the mean free path of the vapor molecules and then push the liquid through the tube at speeds of a car on a highway. The narrow liquid stream creates a sparse vapor cloud, with water molecules spaced far enough apart that they and the reactant gases interact, at most, weakly. Experimentalists, however, confront a host of challenges: nozzle clogging, unstable jetting, searching for vacuum-compatible solutions, measuring low signal levels, and teasing out artifacts because the slender jet is the smallest surface in the vacuum chamber. In this Account, we describe lessons that we are learning as we explore gases (DCl, (HCOOH)2, N2O5) reacting with water molecules and solute ions in the near-interfacial region of these fast-flowing aqueous microjets.

Creation and Reaction of Solvated Electrons at and near the Surface of Water

“…Figure shows the TOF spectrum of evaporating TMA. This spectrum closely mimics the Maxwell–Boltzmann distribution predicted for thermal evaporation of TMA molecules at 235 K. The slightly narrower arrival times likely arise from collisions of TMA with evaporating H 2 O within the water vapor cloud surrounding the jet. , …”

“…This spectrum closely mimics the Maxwell−Boltzmann distribution predicted for thermal evaporation of TMA molecules at 235 K. The slightly narrower arrival times likely arise from collisions of TMA with evaporating H 2 O within the water vapor cloud surrounding the jet. 24,28 We also detected benzyl radical at the parent mass (m/z = 91) with a similar intensity as TMA, as shown in Figure 4a. Three evaporating products may contribute to the m/z = 91 signal recorded by the mass spectrometer: nascent benzyl radicals from the reaction of e s − with BTMA + , toluene from reaction of benzyl and H, and bibenzyl from the selfcombination of benzyl radicals.…”

“…The aqueous microjet solution contains 6.7 M LiBr salt and 0.25 M BTMA + surfactant and is conditioned to pH ∼ 2 to suppress natural hydrolysis of BTMA + by OH – (No TMA or benzyl is observed in the absence of Na atoms at pH = 2). The salty microjet is cooled to 235 K (0.1 Torr vapor pressure, 210 K freezing point) to minimize interference from evaporating water molecules colliding with the sodium atoms or evaporating reaction intermediates . Liquid nitrogen cooled panels maintain the chamber pressure below 1 × 10 –5 Torr.…”

“…The salty microjet is cooled to 235 K (0.1 Torr vapor pressure, 210 K freezing point) to minimize interference from evaporating water molecules colliding with the sodium atoms or evaporating reaction intermediates. 24 Liquid nitrogen cooled panels maintain the chamber pressure below 1 × 10 −5 Torr. The jet travels at 14 m/s and is apertured to limit the observation region to 2.5−5.5 mm from the nozzle tip, corresponding to an observation time of 210 μs.…”

“…The experiments were conducted using a gas-microjet scattering apparatus in a vacuum (Figure S1). 24 The experimental scheme is shown in Figure 1a. A beam of sodium atoms from an oven is directed at a 17 μm radius liquid jet in a vacuum at an average kinetic energy of 19 kJ/mol (Section S3).…”