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.
Overview
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Verification
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Citations
Cites
An Introduction to Statistical Thermodynamics
Hill, T. L., & Gillis, J. (1961) · Physics Today · doi:10.1063/1.3057470 · Cited by 2,207
Ammonia Synthesis from First-Principles Calculations
Honkala, K., Hellman, A., Remediakis, I. N., Logadottir, A., Carlsson, A., Dahl, S., Christensen, C. H., & Nørskov, J. K. (2005) · Science · doi:10.1126/science.1106435 · Cited by 1,336
On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper
Gokhale, A. A., Dumesic, J. A., & Mavrikakis, M. (2008) · Journal of the American Chemical Society · doi:10.1021/ja0768237 · Cited by 984
Reuter, K., & Scheffler, M. (2006) · Physical Review B · doi:10.1103/physrevb.73.045433 · Cited by 359
The Steady State of Heterogeneous Catalysis, Studied by First-Principles Statistical Mechanics
Reuter, K., Frenkel, D., & Scheffler, M. (2004) · Physical Review Letters · doi:10.1103/physrevlett.93.116105 · Cited by 321
Introduction to Statistical Thermodynamics
Siddali, R. G. (1960) · Physics Bulletin · doi:10.1088/0031-9112/11/10/009 · Cited by 283
Arrhenius parameters for rate processes on solid surfaces
Zhdanov, V. P. (1991) · Surface Science Reports · doi:10.1016/0167-5729(91)90011-l · Cited by 254
Blundell, S. (2001) · Magnetism in Condensed Matter · doi:10.1093/oso/9780198505921.005.0005 · Cited by 248
Lombardo, S. J., & Bell, A. T. (1991) · Surface Science Reports · doi:10.1016/0167-5729(91)90004-h · Cited by 238
CO chemisorption on TiO2(110): Oxygen vacancy site influence on CO adsorption
Linsebigler, A., Lu, G., & Yates, J. T. (1995) · The Journal of Chemical Physics · doi:10.1063/1.470005 · Cited by 192
Cited by
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
Chen, B. W. J., Xu, L., & Mavrikakis, M. (2021) · Chemical Reviews · doi:10.1021/acs.chemrev.0c01060 · Cited by 447
Matera, S., Schneider, W. F., Heyden, A., & Savara, A. (2019) · ACS Catalysis · doi:10.1021/acscatal.9b01234 · Cited by 222
Bates, J. S., Bukowski, B. C., Greeley, J., & Gounder, R. (2020) · Chemical Science · doi:10.1039/d0sc02589e · Cited by 117
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
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
Data sources
Bibliographic data: Semantic Scholar, OpenAlex, Crossref.
Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.
