Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene [The effects of hydrogenation on the volatility of organic hydrogen getters]
Abstract
Measurements of equilibrium vapor pressures by effusion thermogravimetry and melting points by differential scanning calorimetry reveal that the melting temperature and equilibrium vapor pressures of 1,4-bis(phenylethynyl)benzene (DEB) do not vary monotonically with the hydrogenation extent. Contrary to intuition which suggests increasing volatility with hydrogenation, results indicate decreasing volatility for the first two hydrogenation steps before a non-monotonic upward trend, in which trans-isomers are less volatile. Insights on structural packing and functional groups were obtained from x-ray diffraction and infrared studies to shed light on the observed variation in the volatility of DEB with hydrogenation. Density functional theory calculations were performed to obtain molecular level information and to establish the thermodynamics of DEB hydrogenation reactions. A major factor influencing the observed melting points and volatility of the hydrogenated intermediate species is identified as the local attractive or repulsive carbon-hydrogen (CH) dipole interactions among the getter molecules in their respective crystal structures. As a result, such collective CH dipole interactions can be used to predict the trends in the volatilities of catalytic hydrogenation processes.
- Authors:
-
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- AWE Plc, Aldermaston, Reading (United Kingdom)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1418965
- Alternate Identifier(s):
- OSTI ID: 1420661
- Report Number(s):
- LLNL-JRNL-727222
Journal ID: ISSN 0021-9606; TRN: US1801323
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 147; Journal Issue: 19; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; organic hydrogen getters; hydrogenation; equilibrium vapor pressures; meting temperatures; volatility
Citation Formats
Sharma, Hom N., Sangalang, Elizabeth A., Saw, Cheng K., Cairns, Gareth A., McLean, William, Maxwell, Robert S., and Dinh, Long N. Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene [The effects of hydrogenation on the volatility of organic hydrogen getters]. United States: N. p., 2017.
Web. doi:10.1063/1.5001205.
Sharma, Hom N., Sangalang, Elizabeth A., Saw, Cheng K., Cairns, Gareth A., McLean, William, Maxwell, Robert S., & Dinh, Long N. Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene [The effects of hydrogenation on the volatility of organic hydrogen getters]. United States. https://doi.org/10.1063/1.5001205
Sharma, Hom N., Sangalang, Elizabeth A., Saw, Cheng K., Cairns, Gareth A., McLean, William, Maxwell, Robert S., and Dinh, Long N. Wed .
"Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene [The effects of hydrogenation on the volatility of organic hydrogen getters]". United States. https://doi.org/10.1063/1.5001205. https://www.osti.gov/servlets/purl/1418965.
@article{osti_1418965,
title = {Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene [The effects of hydrogenation on the volatility of organic hydrogen getters]},
author = {Sharma, Hom N. and Sangalang, Elizabeth A. and Saw, Cheng K. and Cairns, Gareth A. and McLean, William and Maxwell, Robert S. and Dinh, Long N.},
abstractNote = {Measurements of equilibrium vapor pressures by effusion thermogravimetry and melting points by differential scanning calorimetry reveal that the melting temperature and equilibrium vapor pressures of 1,4-bis(phenylethynyl)benzene (DEB) do not vary monotonically with the hydrogenation extent. Contrary to intuition which suggests increasing volatility with hydrogenation, results indicate decreasing volatility for the first two hydrogenation steps before a non-monotonic upward trend, in which trans-isomers are less volatile. Insights on structural packing and functional groups were obtained from x-ray diffraction and infrared studies to shed light on the observed variation in the volatility of DEB with hydrogenation. Density functional theory calculations were performed to obtain molecular level information and to establish the thermodynamics of DEB hydrogenation reactions. A major factor influencing the observed melting points and volatility of the hydrogenated intermediate species is identified as the local attractive or repulsive carbon-hydrogen (CH) dipole interactions among the getter molecules in their respective crystal structures. As a result, such collective CH dipole interactions can be used to predict the trends in the volatilities of catalytic hydrogenation processes.},
doi = {10.1063/1.5001205},
journal = {Journal of Chemical Physics},
number = 19,
volume = 147,
place = {United States},
year = {Wed Nov 15 00:00:00 EST 2017},
month = {Wed Nov 15 00:00:00 EST 2017}
}
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