Coefficients of Evaporation and Gas Phase Diffusion of Low-Volatility Organic Solvents in Nitrogen from Interferometric Study of Evaporating Droplets

Jakubczyk, D.; Derkachov, G.; Duc, Tho Do; Kolwas, K.; Kolwas, M.

doi:10.1021/jp911466e

Cited by 24 publications

(32 citation statements)

References 50 publications

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“…The bias could arise from higher mass oligomeric impurities in the sample, since the measurements at lower temperatures required a considerably longer time to reach equilibrium with respect to temperature and humidity, during which a large volume of the particle already evaporated with corresponding potential enrichment of such impurities. Jakubczyk et al (2010) used an EDB setup as well, and their saturation vapor pressures measured at 298 K compares very favorably with the EDB data of the University of Bristol measurement at this temperature. There is one more data set at lower temperatures available (Wise et al, 1950), obtained by observing the formation of condensates of the vapor on a polished mirror.…”

Section: Resultsmentioning

confidence: 61%

A reference data set for validating vapor pressure measurement techniques: homologous series of polyethylene glycols

Krieger¹,

Siegrist²,

Marcolli³

et al. 2018

Atmos. Meas. Tech.

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Abstract. To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well-established saturation vapor pressures. However, vapor pressures of semivolatile and low-volatility organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of 2. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem, we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H−(O−CH 2 −CH 2 ) n −OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10 −7 to 5 × 10 −2 Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows outlying data to be rejected more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressure values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggests that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about 1 order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest-accuracy data, allowing subsequent extrapolation to atmospheric temperatures.

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Section: Resultsmentioning

confidence: 61%

A reference data set for validating vapor pressure measurement techniques: homologous series of polyethylene glycols

Krieger¹,

Siegrist²,

Marcolli³

et al. 2018

Atmos. Meas. Tech.

View full text Add to dashboard Cite

show abstract

“…Here, γ is the surface free energy, η the viscosity, p 0 the equilibrium vapor pressure, Ω the For our system, the evaporation-condensation terms make negligible contributions to the observed decay constant K of 1000 nm gratings owing to the low vapor pressure of IMC. This conclusion is reached by calculating these terms using known properties: γ = 50 mN/m [12]; Ω ≈ 3 x 10 -28 m 3 ; D G = 0.1 cm 2 /s for organic molecules diffusing in ambient atmosphere [13]; and p 0 is known from vacuum desorption rates of liquid IMC [14]. We find that the A and A' terms are at least 100 times smaller than the observed K. This conclusion is consistent with our observation that IMC gratings decayed at comparable rates in vacuum and in dry N 2 .…”

Section: Driven By Surface Tension An Initially Corrugated Surface Fmentioning

confidence: 99%

Surface Self-Diffusion of an Organic Glass

et al. 2011

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Surface self-diffusion has been measured for an organic glass for the first time. The flattening of 1000 nm surface gratings of liquid indomethacin occurs by viscous flow at 12 K or more above the glass transition temperature and by surface diffusion at lower temperatures. Surface diffusion is at least 10(6) times faster than bulk diffusion, indicating a highly mobile surface. Our data suggest that surface diffusion is the leading mechanism of surface evolution for organic glasses at micrometer to nanometer length scales.

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“…Our analytical model of evaporation used in this work was discussed in details in. 39,41,[47][48][49] It assumes rapid liquid mixing, implicating also no temperature gradients (which turns out to be a good approximation even for relatively fast evaporation rates 50 ) and makes use of the Köhler equation. 51 The Köhler equation formally requires a uniform distribution of particles in liquid, but this kind of parameterization reproduces the observed droplet evolution well.…”

Section: Evolution Of Droplet Sizementioning

confidence: 99%

Formation of Highly Ordered Spherical Aggregates from Drying Microdroplets of Colloidal Suspension

et al. 2015

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The formation of highly ordered spherical aggregates of silica nanoparticles by the evaporation of single droplets of an aqueous colloidal suspension levitated (confined) in the electrodynamic quadrupole trap is reported. The transient and final structures formed during droplet evaporation have been deposited on a silicon substrate and then studied with SEM. Various successive stages of the evaporation-driven aggregation of nanoparticles have been identified: formation of the surface layer of nanoparticles, formation of the highly ordered spherical structure, collapse of the spherical surface layer leading to the formation of densely packed spherical aggregates, and rearrangement of the aggregate into the final structure of a stable 3D quasi-crystal. The evaporation-driven aggregation of submicrometer particles in spherical symmetry leads to sizes and morphologies of the transient and final structures significantly different than in the case of aggregation on a substrate. The numerical model presented in the article allows us to predict and visualize the observed aggregation stages and their dynamics and the final aggregates observed with SEM.

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Coefficients of Evaporation and Gas Phase Diffusion of Low-Volatility Organic Solvents in Nitrogen from Interferometric Study of Evaporating Droplets

Cited by 24 publications

References 50 publications

A reference data set for validating vapor pressure measurement techniques: homologous series of polyethylene glycols

A reference data set for validating vapor pressure measurement techniques: homologous series of polyethylene glycols

Surface Self-Diffusion of an Organic Glass

Formation of Highly Ordered Spherical Aggregates from Drying Microdroplets of Colloidal Suspension

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