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• W2316767583 endingPage "18115" @default.
• W2316767583 startingPage "18109" @default.
• W2316767583 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." @default.
• W2316767583 created "2016-06-24" @default.
• W2316767583 creator A5001366587 @default.
• W2316767583 creator A5043532223 @default.
• W2316767583 date "2012-10-17" @default.
• W2316767583 modified "2023-10-05" @default.
• W2316767583 title "The Entropies of Adsorbed Molecules" @default.
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• W2316767583 doi "https://doi.org/10.1021/ja3080117" @default.
• W2316767583 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/23033909" @default.
• W2316767583 hasPublicationYear "2012" @default.
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