skip to main content

DOE PAGESDOE PAGES

Title: Chemistry and kinetics of the pyrophoric plutonium hydride-air reaction

The chemistry and kinetics of the pyrophoric reaction of the plutonium hydride solid solution (PuH x, 1.9 ≤ x ≤ 3) are derived from pressure-time and gas analysis data obtained after exposure of PuH 2.7 to air in a closed system. The reaction is described in this paper by two sequential steps that result in reaction of all O 2, partial reaction of N 2, and formation of H 2. Hydrogen formed by indiscriminate reaction of N 2 and O 2 at their 3.71:1 M ratio in air during the initial step is accommodated as PuH 3 inside a product layer of Pu 2O 3 and PuN. H 2 is formed by reaction of O 2 and partial reaction of N 2 with PuH 3 during the second step. Both steps of reaction are described by general equations for all values of x. The rate of the first step is proportional to the square of the O 2 pressure, but independent of temperature, x, and N 2 pressure. The second step is a factor of ten slower than step one with its rate controlled by diffusion of O 2 through a boundary layer of product H 2 and unreacted Nmore » 2. Finally, rates and enthalpies of reaction are presented and anticipated effects of reactant configuration on the heat flux are discussed.« less
Authors:
 [1] ; ORCiD logo [2]
  1. Actinide Science Consulting, College Station, TX (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Report Number(s):
LLNL-JRNL-686320
Journal ID: ISSN 0925-8388
Grant/Contract Number:
AC52-07NA27344
Type:
Accepted Manuscript
Journal Name:
Journal of Alloys and Compounds
Additional Journal Information:
Journal Volume: 698; Journal ID: ISSN 0925-8388
Publisher:
Elsevier
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; plutonium kinetics hydride
OSTI Identifier:
1366943
Alternate Identifier(s):
OSTI ID: 1412567

Haschke, John M., and Dinh, Long N.. Chemistry and kinetics of the pyrophoric plutonium hydride-air reaction. United States: N. p., Web. doi:10.1016/j.jallcom.2016.12.162.
Haschke, John M., & Dinh, Long N.. Chemistry and kinetics of the pyrophoric plutonium hydride-air reaction. United States. doi:10.1016/j.jallcom.2016.12.162.
Haschke, John M., and Dinh, Long N.. 2016. "Chemistry and kinetics of the pyrophoric plutonium hydride-air reaction". United States. doi:10.1016/j.jallcom.2016.12.162. https://www.osti.gov/servlets/purl/1366943.
@article{osti_1366943,
title = {Chemistry and kinetics of the pyrophoric plutonium hydride-air reaction},
author = {Haschke, John M. and Dinh, Long N.},
abstractNote = {The chemistry and kinetics of the pyrophoric reaction of the plutonium hydride solid solution (PuHx, 1.9 ≤ x ≤ 3) are derived from pressure-time and gas analysis data obtained after exposure of PuH2.7 to air in a closed system. The reaction is described in this paper by two sequential steps that result in reaction of all O2, partial reaction of N2, and formation of H2. Hydrogen formed by indiscriminate reaction of N2 and O2 at their 3.71:1 M ratio in air during the initial step is accommodated as PuH3 inside a product layer of Pu2O3 and PuN. H2 is formed by reaction of O2 and partial reaction of N2 with PuH3 during the second step. Both steps of reaction are described by general equations for all values of x. The rate of the first step is proportional to the square of the O2 pressure, but independent of temperature, x, and N2 pressure. The second step is a factor of ten slower than step one with its rate controlled by diffusion of O2 through a boundary layer of product H2 and unreacted N2. Finally, rates and enthalpies of reaction are presented and anticipated effects of reactant configuration on the heat flux are discussed.},
doi = {10.1016/j.jallcom.2016.12.162},
journal = {Journal of Alloys and Compounds},
number = ,
volume = 698,
place = {United States},
year = {2016},
month = {12}
}