Binary nucleation rates for ethanol/water mixtures in supersonic Laval nozzles: Analyses by the first and second nucleation theorems

Tanimura, Shinobu; Pathak, Harshad; Wyslouzil, Barbara E.

doi:10.1063/1.4826652

Title: Binary nucleation rates for ethanol/water mixtures in supersonic Laval nozzles: Analyses by the first and second nucleation theorems

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Abstract

We performed pressure trace measurements and small angle x-ray scattering measurements to determine the vapor-liquid nucleation rates of EtOH/H{sub 2}O mixtures including pure EtOH and pure H{sub 2}O in two supersonic Laval nozzles with different expansion rates. The nucleation rates varied from 0.9 × 10{sup 17} to 16 × 10{sup 17} cm{sup −3} s{sup −1} over the temperature range of 210 K to 230 K, EtOH activity range of 0 to 11.6, and H{sub 2}O activity range of 0 to 124. The first and second nucleation theorems were applied to the nucleation rates to estimate the sizes, compositions, and excess energies of the critical clusters. The critical clusters contained from 4 to 15 molecules for pure H{sub 2}O and EtOH/H{sub 2}O clusters, and from 16 to 23 molecules for pure EtOH clusters. Comparing the excess energies of the pure H{sub 2}O critical clusters with the results of a quantum-chemistry calculation suggested that the pre-factor of the theoretical nucleation rate is almost constant regardless of the monomer concentration. One possible explanation for this result is that cooling of the critical clusters limits the nucleation rate under the highly supersaturated conditions. The results of the analyses also yielded the relation between themore »« less

Authors:

Tanimura, Shinobu; Pathak, Harshad ^[1]; Wyslouzil, Barbara E. ^[1]

William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State University, 140 West 19th Av., Columbus, Ohio 43210 (United States)

Publication Date:: Thu Nov 07 00:00:00 EST 2013

OSTI Identifier:: 22251544

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 139; Journal Issue: 17; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ADSORPTION; ETHANOL; LIQUIDS; MIXTURES; NUCLEATION; SMALL ANGLE SCATTERING; SURFACE ENERGY; SURFACE TENSION; SURFACES; TEMPERATURE RANGE; WATER; X-RAY DIFFRACTION

Citation Formats


                    Tanimura, Shinobu, Pathak, Harshad, Wyslouzil, Barbara E., and Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210. Binary nucleation rates for ethanol/water mixtures in supersonic Laval nozzles: Analyses by the first and second nucleation theorems.  United States: N. p., 2013. 
        Web.  doi:10.1063/1.4826652.

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                    Tanimura, Shinobu, Pathak, Harshad, Wyslouzil, Barbara E., & Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210. Binary nucleation rates for ethanol/water mixtures in supersonic Laval nozzles: Analyses by the first and second nucleation theorems.  United States.  https://doi.org/10.1063/1.4826652

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                    Tanimura, Shinobu, Pathak, Harshad, Wyslouzil, Barbara E., and Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210. 2013.  
        "Binary nucleation rates for ethanol/water mixtures in supersonic Laval nozzles: Analyses by the first and second nucleation theorems".  United States.  https://doi.org/10.1063/1.4826652.

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@article{osti_22251544,

  title        = {Binary nucleation rates for ethanol/water mixtures in supersonic Laval nozzles: Analyses by the first and second nucleation theorems},

  author       = {Tanimura, Shinobu and Pathak, Harshad and Wyslouzil, Barbara E. and Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210},

  abstractNote = {We performed pressure trace measurements and small angle x-ray scattering measurements to determine the vapor-liquid nucleation rates of EtOH/H{sub 2}O mixtures including pure EtOH and pure H{sub 2}O in two supersonic Laval nozzles with different expansion rates. The nucleation rates varied from 0.9 × 10{sup 17} to 16 × 10{sup 17} cm{sup −3} s{sup −1} over the temperature range of 210 K to 230 K, EtOH activity range of 0 to 11.6, and H{sub 2}O activity range of 0 to 124. The first and second nucleation theorems were applied to the nucleation rates to estimate the sizes, compositions, and excess energies of the critical clusters. The critical clusters contained from 4 to 15 molecules for pure H{sub 2}O and EtOH/H{sub 2}O clusters, and from 16 to 23 molecules for pure EtOH clusters. Comparing the excess energies of the pure H{sub 2}O critical clusters with the results of a quantum-chemistry calculation suggested that the pre-factor of the theoretical nucleation rate is almost constant regardless of the monomer concentration. One possible explanation for this result is that cooling of the critical clusters limits the nucleation rate under the highly supersaturated conditions. The results of the analyses also yielded the relation between the surface energy and the composition of the critical clusters, where the latter are predicted to consist only of surface molecules. Applying this relationship to the EtOH/H{sub 2}O bulk liquid mixtures, we estimated the EtOH mole fraction in the surface layer and found it is higher than that derived from the surface tension based on the Gibbs adsorption equation when the EtOH mole fraction in the liquid is higher than about 0.2 mol/mol. This discrepancy was attributed to the existence of the EtOH depletion layer just below the surface layer of the liquid.},

  doi          = {10.1063/1.4826652},

  url          = {https://www.osti.gov/biblio/22251544},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 17,

  volume       = 139,

  place        = {United States},

  year         = {Thu Nov 07 00:00:00 EST 2013},

  month        = {Thu Nov 07 00:00:00 EST 2013}

}

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