The DOI matches its Crossref record; 17 of the 17 references it cites were found in a registry or an index.
The Entropies of Adsorbed Molecules
Abstract
Adsorbed molecules are involved in many reactions on solid surface that are of great technological importance. As such, there has been tremendous effort worldwide to learn how to predict reaction rates and equilibrium constants for reactions involving adsorbed molecules. Theoretical calculation of both the rate and equilibrium constants for such reactions requires knowing the entropy and enthalpy of the adsorbed molecule. While much effort has been devoted to measuring and calculating the enthalpies of well-defined adsorbates, few measurements of the entropies of adsorbates have been reported. We present here a new way to determine the standard entropies of adsorbed molecules (S(ad)(0)) on single crystal surfaces from temperature programmed desorption data, prove its accuracy by comparison to entropies measured by equilibrium methods, and apply it to published data to extract new entropies. Most importantly, when combined with reported entropies, we find that at high coverage, they linearly track the entropy of the gas-phase molecule at the same temperature (T), such that S(ad)(0)(T) = 0.70 S(gas)(0)(T) - 3.3R (R = the gas constant), with a standard deviation of only 2R over a range of 50R. These entropies, which are ~2/3 of the gas, are huge compared to most theoretical predictions. This result can be extended to reliably predict prefactors in the Arrhenius rate constant for surface reactions involving such species, as proven here for desorption.
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Paolucci, C., Parekh, A. A., Khurana, I., Di Iorio, J. R., Li, H., Albarracin Caballero, J. D., Shih, A. J., Anggara, T., Delgass, W. N., Miller, J. T., et al. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.6b02651 · Cited by 784
Nanoparticle decoration with surfactants: Molecular interactions, assembly, and applications
Heinz, H., Pramanik, C., Heinz, O., Ding, Y., Mishra, R. K., Marchon, D., Flatt, R. J., Estrela-Lopis, I., Llop, J., Moya, S., et al. (2017) · Surface Science Reports · doi:10.1016/j.surfrep.2017.02.001 · Cited by 608
Wellendorff, J., Silbaugh, T. L., Garcia-Pintos, D., Nørskov, J. K., Bligaard, T., Studt, F., & Campbell, C. T. (2015) · Surface Science · doi:10.1016/j.susc.2015.03.023 · Cited by 572
Self-citationMicrokinetic Modeling: A Tool for Rational Catalyst Design
Motagamwala, A. H., & Dumesic, J. A. (2021) · Chemical Reviews · doi:10.1021/acs.chemrev.0c00394 · Cited by 485
Computational Methods in Heterogeneous Catalysis
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Metadata
- Authors
- Campbell, C. T., & Sellers, J. R. V.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-10-17
- Volume
- 134
- Issue
- 43
- Pages
- 18109-18115
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2316767583
- Cited by
- 454
- References
- 17
- FWCI
- 7.87
- Type
- journal article
- Language
- en
- Open access
- closed
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