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Title: Kinetics of H2 Uptake by 1,4-bis(phenylethynyl)benzene-based Hydrogen Getters

 [1];  [1]
  1. Los Alamos National Laboratory
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
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Report Number(s):
DOE Contract Number:
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Resource Relation:
Conference: International Hydrogen Conference ; 2016-09-11 - 2016-09-14 ; Moran, Wyoming, United States
Country of Publication:
United States

Citation Formats

Safarik, Douglas Joseph, and Janicke, Michael Timothy. Kinetics of H2 Uptake by 1,4-bis(phenylethynyl)benzene-based Hydrogen Getters. United States: N. p., 2016. Web.
Safarik, Douglas Joseph, & Janicke, Michael Timothy. Kinetics of H2 Uptake by 1,4-bis(phenylethynyl)benzene-based Hydrogen Getters. United States.
Safarik, Douglas Joseph, and Janicke, Michael Timothy. 2016. "Kinetics of H2 Uptake by 1,4-bis(phenylethynyl)benzene-based Hydrogen Getters". United States. doi:.
title = {Kinetics of H2 Uptake by 1,4-bis(phenylethynyl)benzene-based Hydrogen Getters},
author = {Safarik, Douglas Joseph and Janicke, Michael Timothy},
abstractNote = {},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 9

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  • 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 performedmore » 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.« less
  • The aging of hermetically sealed systems is often accompanied by the gradual production of hydrogen gas that is a result of the decay of environmental gases and the degradation of organic materials. In particular, the oxygen, water, hydrogen ''equilibrium'' is affected by the removal of oxygen due the oxidation of metals and organic materials. This shift of the above ''equilibrium'' towards the formation of hydrogen gas, particularly in crevices, may eventually reach an explosive level of hydrogen gas or degrade metals by hydriding them. The latter process is generally delayed until the oxidizing species are significantly reduced. Organic hydrogen gettersmore » introduced by Allied Signal Aerospace Company, Kansas City Division have proven to be a very effective means of preventing hydrogen gas accumulation in sealed containers. These getters are relatively unaffected by air and environmental gases. They can be packaged in a variety of ways to fit particular needs such as porous pellets, fine or coarse [gravel] powder, or loaded into silicone rubber. The hydrogen gettering reactions are extremely irreversible since the hydrogen gas is converted into an organic hydrocarbon. These getters are based on the palladium-catalyzed hydrogenation of triple bonds to double and then single bonds in aromatic aryl compounds. DEB (1,4 bis (phenyl ethynyl) benzene) typically mixed with 25% by weight carbon with palladium (1% by weight of carbon) is one of the newest and best of these organic hydrogen getters. The reaction mechanisms are complex involving solid state reaction with a heterogeneous catalyst leading to the many intermediates, including mixed alkyl and aryl hydrocarbons with the possibilities of many isomers. The reaction kinetics mechanisms are also strongly influenced by the form in which they are packaged. For example, the hydriding rates for pellets and gravel have a strong dependence on reaction extent (i.e., DEB reduction) and a kinetic order in pressure of 0.76. Silicone rubber based DEB getters hydride at a much lower rate, have little dependence on reaction extent, have a higher kinetic order in pressure (0.87), and have a lower activation energy. The kinetics of the reaction as a function of hydrogen pressure, stoichiometry, and temperature for hydrogen and deuterium near ambient temperature (0 to 75 C) for pressures near or below 100 Pa over a wide range (in some cases, the complete) hydrogenation range are presented along with multi-dimensional rate models.« less
  • Organic hydrogen getters are utilized to minimize hydrogen accumulation in sealed systems where such build up could produce either a safety problem from pressure build up or corrosion problem due the hydriding of metals contained in the sealed vessel. DEB (1,4 bis (phenyl ethynyl) benzene) is a hydrogen getter that is based on the palladium catalyzed hydrogenation of triple bonds to single bonds in aromatic aryl compound. DEB is a getter mixed with 25% carbon and 1% Pd and pressed into pellets with some porosity. The reaction mechanisms are complex involving solid state reactions with a heterogeneous catalyst leading tomore » the many intermediates.« less
  • Abstract not provided.
  • Nuclear Materials Management (NMM) of WSRC has recently installed the capability to perform both non-destructive and destructive examination of 3013 containers of Pu oxide in accordance with DOE-STD-3013. The containers will be opened and the oxide will be sampled for analysis. The remaining bulk oxide must then be safely stored in a non-3013-compliant configuration. Available processing equipment and controls cannot prevent the oxide from adsorbing moisture during this process. Subsequent radiolysis of moisture during storage may generate combustible quantities of gases while waiting final processing, and satisfying DOE Interim Safe Storage Criteria (ISSC) would require that storage containers be ventedmore » at impractical frequencies. With support from an independent National Laboratory, WSRC/NMM has demonstrated that a commercial hydrogen getter material will effectively prevent the accumulation of combustible gas concentrations. A project overview, including storage requirements and strategies, as well as getter technology, current test results, and anticipated future developments will be addressed.« less