DOI: 10.1063/1.2400235. n -alkanes on Pt(111) and on C(0001)∕Pt(111): Chain length dependence of kinetic desorption parameters

n -alkanes on Pt(111) and on C(0001)∕Pt(111): Chain length dependence of kinetic desorption parameters

10.1063/1.2400235

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

We have measured the desorption of seven small n-alkanes (CNH2N+2, N=1–4,6,8,10) from the Pt(111) and C(0001) surfaces by temperature programed desorption. We compare these results to our recent study of the desorption kinetics of these molecules on MgO(100) [J. Chem. Phys. 122, 164708 (2005)]. There we showed an increase in the desorption preexponential factor by several orders of magnitude with increasing n-alkane chain length and a linear desorption energy scaling with a small y-intercept value. We suggest that the significant increase in desorption prefactor with chain length is not particular to the MgO(100) surface, but is a general effect for desorption of the small n-alkanes. This argument is supported by statistical mechanical arguments for the increase in the entropy gain of the molecules upon desorption. In this work, we demonstrate that this hypothesis holds true on both a metal surface and a graphite surface. We observe an increase in prefactor by five orders of magnitude over the range of n-alkane chain lengths studied here. On each surface, the desorption energies of the n-alkanes are found to increase linearly with the molecule chain length and have a small y-intercept value. Prior results of other groups have yielded a linear desorption energy scaling with chain length that has unphysically large y-intercept values. We demonstrate that by allowing the prefactor to increase according to our model, a reanalysis of their data resolves this y-intercept problem to some degree.

Bibliography

Tait, S. L., DohnÃ¡lek, Z., Campbell, C. T., & Kay, B. D. (2006). n -alkanes on Pt(111) and on C(0001)âPt(111): Chain length dependence of kinetic desorption parameters. The Journal of Chemical Physics, 125(23).

Authors 4

Steven L. Tait (first)
Zdenek Dohnálek (additional)
Charles T. Campbell (additional)
Bruce D. Kay (additional)

References 37 Referenced 184

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Dates

Type	When
Created	18 years, 8 months ago (Dec. 21, 2006, 10:37 a.m.)
Deposited	2 years, 2 months ago (June 26, 2023, 1:49 a.m.)
Indexed	4 days, 12 hours ago (Aug. 24, 2025, 6:57 p.m.)
Issued	18 years, 8 months ago (Dec. 20, 2006)
Published	18 years, 8 months ago (Dec. 20, 2006)
Published Online	18 years, 8 months ago (Dec. 20, 2006)
Published Print	18 years, 8 months ago (Dec. 21, 2006)

Funders 0

None

BibTeX

@article{Tait_2006, title={n -alkanes on Pt(111) and on C(0001)∕Pt(111): Chain length dependence of kinetic desorption parameters}, volume={125}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.2400235}, DOI={10.1063/1.2400235}, number={23}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Tait, Steven L. and Dohnálek, Zdenek and Campbell, Charles T. and Kay, Bruce D.}, year={2006}, month=dec }

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