Effects of Li2O Thickness and Moisture Content on LiH Hydrolysis Kinetics in Slightly Humidified Argon

The hydrolysis kinetics of polycrystalline lithium hydride (LiH) in argon at various low humidities was measured by gravimetry and Raman spectroscopy with ambient water concentration ranging from 200 to 1200 ppm. The results showed that LiH hydrolysis curve revealed a paralinear shape, which was attributed to two different reaction stages that forming different products as explained by the 'Layer Diffusion Control' model. Based on the model, a novel two-stage rate equation for LiH hydrolysis reactions was developed and used to fit the experimental data for determination of Li2O steady thickness Hs and the ultimate hydrolysis rate vs. The fitted data presented a rise of Hs as ambient water concentration cw increased. However, in spite of the negative effect imposed by Hs increasing, the upward trend of vs remained, which implied that water concentration, rather than Li2O thickness, played a predominant role in LiH hydrolysis kinetics. In addition, the proportional relationship between vsHs and cw predicted by rate equation and confirmed by gravimetric data validated the model in such conditions.





References:
[1] C.L. Haertling, R.J. Hanrahan, and J.R. Tesmer, Hydrolysis Studies of
Polycrystalline Lithium Hydride. Journal of Physical Chemistry C, 2007. vol. 111, no. 4, pp. 1716-1724.
[2] J. Lu, Z.Z. Fang, and H.Y. Sohn, A hybrid method for hydrogen storage
and generation from water. Journal of Power Sources, 2007. vol. 172, no. 2, pp. 853-858.
[3] C.L. Haertling, J.R.J. Hanrahan, and R. Smith, A literature review of
reactions and kinetics of lithium hydride hydrolysis. Journal of Nuclear
Materials, 2006. vol. 349, no. 1-2, pp. 195-233.
[4] J.F. McLaughlin, and S.S. Cristy, Composition of corrosion films on
lithium hydride surfaces after exposure to air. Oak Ridge Y-12 Plant
report Y-1929, Oak Ridge Y-12 Plant, 1974.
[5] W.D. Machin, and F.C. Tompkins, Trans. Faraday Soc., 1966. vol. 62,
pp. 2205.
[6] C.E. Holcombe, and G.L. Powell, Some observations on the reaction layer of LiOH on LiH. Journal of Nuclear Materials, 1973. vol. 47, no. 1, pp. 121-124.
[7] S.S. Cristy, SIMS Depth profiling of an insulating air-sensitive material.
1987, Oak Ridge Y-12 Plant.
[8] R.P. Awbery, D.A. Broughton, and S.C. Tsang, In situ observation of
lithium hydride hydrolysis by DRIFT spectroscopy. Journal of Nuclear Materials, 2008. vol. 373, no. 1-3, pp. 94-102.
[9] M. Balooch, L.N. Dinh, and D.F. Calef, The reaction kinetics of lithium
salt with water vapor. Journal of Nuclear Materials, 2002. vol. 303, no. 2-3, pp. 200-209.
[10] G.L. Powell, et al., The Spectropus System: Remote Sampling Accessories for Reflectance, Emission, and Transmission Analysis Using
Fourier Transform Infrared Spectroscopy. Appl. Spectrosc., 1992. vol. 46,
no. 1, pp. 111-125.
[11] L.N. Dinh, et al., The effects of moisture on LiD single crystals studied by
temperature-programmed decomposition. Journal of Nuclear Materials,
2001. vol. 295, no. 2-3, pp. 193-204.
[12] D. Broughton, Hydrolysis of lithium hydride. 2001, The University of
Reading: Reading, UK.
[13] K.V. Wilson Jr, B.M. Patterson, and J. Phillips, Microbalance study of the
corrosion kinetics of lithium hydride by water. Journal of Nuclear
Materials, 2008. vol. 374, no. 1-2, pp. 229-240.
[14] J. Phillips, et al., Generation of a Highly Effective Corrosion Barrier on
LiH Surfaces. Journal of Physical Chemistry C, 2008. vol. 112, no. 49,
pp. 19405-19411.
[15] J. Tanski, Analysis of a New Reaction Mechanism for Hydrolysis of LiH.
2000, Los Alamos National Laboratory.