Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene [The effects of hydrogenation on the volatility of organic hydrogen getters]

Sharma, Hom N.; Sangalang, Elizabeth A.; Saw, Cheng K.; Cairns, Gareth A.; McLean, William; Maxwell, Robert S.; Dinh, Long N.

doi:10.1063/1.5001205

Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene [The effects of hydrogenation on the volatility of organic hydrogen getters]

Journal Article · Tue Nov 14 23:00:00 EST 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5001205· OSTI ID:1418965

Sharma, Hom N. ^[1]; Sangalang, Elizabeth A. ^[1]; Saw, Cheng K. ^[1]; Cairns, Gareth A. ^[2]; McLean, William ^[1]; Maxwell, Robert S. ^[1]; Dinh, Long N. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
AWE Plc, Aldermaston, Reading (United Kingdom)

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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1418965

Report Number(s):: LLNL-JRNL--727222

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 147; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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