Aaron H. Persad

Statistical rate theory examination of ethanol evaporation.

A series of low-temperature (246 < T(I)(L) < 267 K) steady-state ethanol evaporation experiments have been conducted to determine the saturation vapor pressure of metastable ethanol. The measured interfacial conditions have been used with statistical rate theory (SRT) to develop an expression for the saturation vapor pressure as a function of temperature, f(srt)(eth). This expression is shown to be thermodynamically consistent because it gives predictions of both the evaporative latent heat and the liquid constant-pressure specific heat that are in agreement with independent measurements of these properties. In each experiment, the interfacial vapor temperature was measured to be greater than the interfacial liquid temperature, [triple bond]DeltaT(I)(LV). When f(srt)(eth) is used in SRT to predict DeltaT(I)(LV), the results are shown to be consistent with the measurements. Other expressions for the saturation vapor pressure that are in the literature are examined and found to be thermodynamically inconsistent and do not lead to valid predictions of DeltaT(I)(LV).

Condensation in One-Dimensional Dead-End Nanochannels

Phase change at the nanoscale is at the heart of many biological and geological phenomena. The recent emergence and global implications of unconventional oil and gas production from nanoporous shale further necessitate a higher understanding of phase behavior at these scales. Here, we directly observe condensation and condensate growth of a light hydrocarbon (propane) in discrete sub-100 nm (∼70 nm) channels. Two different condensation mechanisms at this nanoscale are distinguished, continuous growth and discontinuous growth due to liquid bridging ahead of the meniscus, both leading to similar net growth rates. The growth rates agree well with those predicted by a suitably defined thermofluid resistance model. In contrast to phase change at larger scales (∼220 and ∼1000 nm cases), the rate of liquid condensate growth in channels of sub-100 nm size is found to be limited mainly by vapor flow resistance (∼70% of the total resistance here), with interface resistance making up the difference. The condensation-induced vapor flow is in the transitional flow regime (Knudsen flow accounting for up to 13% of total resistance here). Collectively, these results demonstrate that with confinement at sub-100 nm scales, such as is commonly found in porous shale and other applications, condensation conditions deviate from the microscale and larger bulk conditions chiefly due to vapor flow and interface resistances.

Source of temperature and pressure pulsations during sessile droplet evaporation into multicomponent atmospheres.

During sessile droplet evaporation, studies with IR thermography and shadowgraphs have indicated temperature pulsations. We confirm those observations with microthermocouples, but microthermocouples also indicate temperature pulsations in the atmosphere of the droplet. The pressure in this atmosphere pulsated as well and was correlated with the temperature pulsations in the droplet. Also, we find that if a droplet evaporates into its own vapor, there are no temperature or pressure pulsations. The pulsations occur only if the droplet evaporates into an atmosphere with a component having a heat of solution with the droplet when it adsorbs-absorbs. None of the currently proposed mechanisms for the temperature pulsations provide an explanation for the coupling between the temperature pulsations in the droplet and the vapor-phase pressure pulsations, and for the absence of the pulsations when the system is single-component. As a mechanism for the pulsations, we propose that when a droplet is exposed to an atmosphere containing a component that has a heat of solution with the droplet, energy will be released from adsorption-absorption. This energy will cause pulsations in the evaporation flux, and these pulsations could cause the observed temperature and pressure pulsations. We examine this mechanism by showing that, if the measured temperature pulsations in a water droplet exposed to a methanol atmosphere are used as the input to a theory of evaporation kinetics (statistical rate theory), the pressure pulsations of the water vapor in the methanol atmosphere are predicted and agree with those measured with a quadrupole mass analyzer. When the inputs and outputs are reversed in the theory, we find that the temperature pulsations in the droplet are correctly predicted from the measured water vapor pulsations in the atmosphere.

Capillary Condensation in 8 nm Deep Channels

Condensation on the nanoscale is essential to understand many natural and synthetic systems relevant to water, air, and energy. Despite its importance, the underlying physics of condensation initiation and propagation remain largely unknown at sub-10 nm, mainly due to the challenges of controlling and probing such small systems. Here we study the condensation of n-propane down to 8 nm confinement in a nanofluidic system, distinct from previous studies at ∼100 nm. The condensation initiates significantly earlier in the 8 nm channels, and it initiates from the entrance, in contrast to channels just 10 times larger. The condensate propagation is observed to be governed by two liquid-vapor interfaces with an interplay between film and bridging effects. We model the experimental results using classical theories and find good agreement, demonstrating that this 8 nm nonpolar fluid system can be treated as a continuum from a thermodynamic perspective, despite having only 10-20 molecular layers.

Chapter 17 – Thermal Origins

This chapter provides detailed examples of thermo-gravitational, thermo-capillary and thermo-solutal instabilities. When a fluid is confined and in normal Earth gravity, the fluid configuration is vertically anti-symmetric. If suddenly exposed to weightlessness, the fluid will transition to a symmetric configuration over a period of time. Thermo-capillary instabilities have been observed during sessile droplet evaporation in the absence of buoyancy-driven convection and radiation. When the droplet rests on a thermally insulating substrate, no thermo-capillary convection is measured. However, if the substrate is thermally conductive, a transition to thermo-capillary flow has been observed and the transition depends on the evaporation rate. When a droplet evaporates into multicomponent atmospheres, thermo-solutal instabilities arise if one of the atmosphere species has a heat of solution with the droplet component. The thermo-solutal instabilities appear as temperature and pressure pulsations in the liquid and in the vapor phases that are coupled by the evaporation flux.