Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

Luo, Weifang; Cowgill, Donald F.

doi:10.1021/acs.jpcc.5b06848

Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

Journal Article · Wed Jul 22 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b06848· OSTI ID:1235301

Luo, Weifang ^[1]; Cowgill, Donald F. ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H₂ + PdD and D₂ + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H₂/atm cm² s is found for H₂ + PdD at 298 K, 1.4 times higher than that for D₂ + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1235301

Report Number(s):: SAND--2015-4492J; 590571

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 32 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (11)

Zustandsdiagramm und thermodynamisches Verhalten der Systeme Pd/H ₂ und Pd/D ₂ bei normalen Temperaturen; H/D-Trenneffekte Wicke, E.; Nernst, G. H. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 68, Issue 3 https://doi.org/10.1002/bbpc.19640680303	journal	April 1964
Interaction of Hydrogen Isotopes with Transition Metals and Intermetallic Compounds Andreev, B. M.; Magomedbekov, E. P.; Sicking, G. H. Springer Tracts in Modern Physics https://doi.org/10.1007/BFb0045240	book	January 1996
Studies of isotopic exchange between gaseous hydrogen and palladium hydride powder Foltz, G. Journal of Catalysis, Vol. 108, Issue 2 https://doi.org/10.1016/0021-9517(87)90189-8	journal	December 1987
Hydrogen isotope exchange and separation in gas-solid phase systems Sicking, G.; Albers, P.; Magomedbekov, E. Journal of the Less Common Metals, Vol. 89, Issue 2 https://doi.org/10.1016/0022-5088(83)90347-8	journal	February 1983
Calorimetric enthalpies of absorption and desorption of protium and deuterium by palladium Flanagan, Ted B.; Luo, W.; Clewley, J. D. Journal of the Less Common Metals, Vol. 172-174 https://doi.org/10.1016/0022-5088(91)90431-3	journal	August 1991
Adsorption of hydrogen on Pd(100) Behm, R. J.; Christmann, K.; Ertl, G. Surface Science, Vol. 99, Issue 2 https://doi.org/10.1016/0039-6028(80)90396-9	journal	September 1980
NMR Measurement of Exchange of Deuterium between Palladium–Deuteride and Deuterium Gas Corey, Robert L.; Cowgill, Donald F.; Conradi, Mark S. The Journal of Physical Chemistry C, Vol. 116, Issue 6 https://doi.org/10.1021/jp210839t	journal	February 2012
Thermodynamic and Kinetic Characterization of Hydrogen−Deuterium Exchange in β-Phase Palladium Luo, Weifang; Cowgill, Donald F.; Causey, Rion A. The Journal of Physical Chemistry B, Vol. 113, Issue 39 https://doi.org/10.1021/jp903633b	journal	September 2009
Equilibrium Isotope Effect for Hydrogen Absorption in Palladium Luo, Weifang; Cowgill, Donald F.; Causey, Rion A. The Journal of Physical Chemistry C, Vol. 113, Issue 46 https://doi.org/10.1021/jp905614x	journal	October 2009
Some Thermodynamic Properties of the H ¹ H ² , H ² H ² Molecules and Compounds Containing the H ² Atom Urey, Harold C.; Rittenberg, D. The Journal of Chemical Physics, Vol. 1, Issue 2 https://doi.org/10.1063/1.1749265	journal	February 1933
Role of molecular diffusion in the theory of gas flow through crimped-capillary leaks Bach, H. T.; Meyer, B. A.; Tuggle, D. G. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 21, Issue 3 https://doi.org/10.1116/1.1569924	journal	May 2003

Cited By (2)

Molecular Calcium Hydride: Dicalcium Trihydride Cation Stabilized by a Neutral NNNN-Type Macrocyclic Ligand Leich, Valeri; Spaniol, Thomas P.; Maron, Laurent Angewandte Chemie International Edition, Vol. 55, Issue 15 https://doi.org/10.1002/anie.201600552	journal	March 2016
Calcium Hydride Cation [CaH] ⁺ Stabilized by an NNNN-type Macrocyclic Ligand: A Selective Catalyst for Olefin Hydrogenation Schuhknecht, Danny; Lhotzky, Carolin; Spaniol, Thomas P. Angewandte Chemie International Edition, Vol. 56, Issue 40 https://doi.org/10.1002/anie.201706848	journal	August 2017

Similar Records

Thermodynamic and kinetic characterization of H-D exchange in Pd and Pd alloys.

Conference · Wed Sep 01 00:00:00 EDT 2010 · OSTI ID:1030323

Laser vaporization/rare gas matrix-isolation electron spin resonance studies of PdH sup + sub 2 , PdD sup + sub 2 , PdH, and PdD: Theoretical investigation of PdH sup + sub 2

Journal Article · Wed Feb 28 23:00:00 EST 1990 · Journal of Chemical Physics; (USA) · OSTI ID:7166228

NMR comparisons of nanocrystalline and coarse-grained palladium hydride and deuteride.

Journal Article · Fri Jan 31 23:00:00 EST 2003 · Phys. Rev. B · OSTI ID:961182

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

Citation Formats

References (11)

Cited By (2)

Similar Records

Related Subjects