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Determination of diffusion coefficients of hydrogen in fused silica between 296 and 523 K by Raman spectroscopy and application of fused silica capillaries in studying redox reactions

L. Shang·I-Ming Chou·W. Lu·Robert Burruss·Y. Zhang
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Abstract

Diffusion coefficients ( D ) of hydrogen in fused silica capillaries (FSC) were determined between 296 and 523 K by Raman spectroscopy using CO 2 as an internal standard. FSC capsules (3.25 × 10 −4 m OD, 9.9 × 10 −5 m ID, and ∼0.01 m long) containing CO 2 and H 2 were prepared and the initial relative concentrations of hydrogen in these capsules were derived from the Raman peak-height ratios between H 2 (near 587 cm −1 ) and CO 2 (near 1387 cm −1 ). The sample capsules were then heated at a fixed temperature ( T ) at one atmosphere to let H 2 diffuse out of the capsule, and the changes of hydrogen concentration were monitored by Raman spectroscopy after quench. This process was repeated using different heating durations at 296 (room T ), 323, 375, 430, 473, and 523 K; the same sample capsule was used repeatedly at each temperature. The values of D (in m 2 s −1 ) in FSC were obtained by fitting the observed changes of hydrogen concentration in the FSC capsule to an equation based on Fick’s law. Our D values are in good agreement with the more recent of the two previously reported experimental data sets, and both can be represented by: ln D = - ( 16.471 ± 0.035 ) - 44589 ± 139 RT ( R 2 = 0.99991 ) "> lnD=-(16.471±0.035)-44589±139RT(R2=0.99991) where R is the gas constant (8.3145 J/mol K), T in Kelvin, and errors at 1 σ level. The slope corresponds to an activation energy of 44.59 ± 0.14 kJ/mol. The D in FSC determined at 296 K is about an order of magnitude higher than that in platinum at 723 K, indicating that FSC is a suitable membrane for hydrogen at temperature between 673 K and room temperature, and has a great potential for studying redox reactions at these temperatures, especially for systems containing organic material and/or sulphur.

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L. Shang, I-Ming Chou, W. Lu, Robert Burruss, Y. Zhang. 2009. Determination of diffusion coefficients of hydrogen in fused silica between 296 and 523 K by Raman spectroscopy and application of fused silica capillaries in studying redox reactions. https://doi.org/10.1016/j.gca.2009.06.001

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