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Updated: Aug 12, 2025

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Analysis of Temperature-Programmed Desorption via Equilibrium Thermodynamics.

Michael Schmid1, Gareth S Parkinson1, Ulrike Diebold1

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|January 31, 2023
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Summary

This study introduces a novel thermodynamic method for analyzing temperature-programmed desorption (TPD) experiments, simplifying the determination of adsorption energies and kinetics. The approach offers a more straightforward analysis of surface-adsorbate interactions.

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Area of Science:

  • Surface science
  • Physical chemistry
  • Materials science

Background:

  • Traditional analysis of temperature-programmed desorption (TPD) experiments relies on complex methods like the Polanyi-Wigner equation or transition-state theory.
  • Determining the pre-exponential factor in TPD analysis is often challenging and problematic.
  • Existing methods lack straightforwardness in analyzing surface-adsorbate interactions.

Purpose of the Study:

  • To present a new, equilibrium thermodynamics-based method for analyzing TPD experiments.
  • To simplify the determination of adsorption energies and kinetics in TPD.
  • To provide a more accessible approach to understanding surface-adsorbate interactions.

Main Methods:

  • Development of equations for desorption rate based on equilibrium thermodynamics.
  • Analysis of three surface-adsorbate interaction models: 2D ideal hard-sphere gas, ideal lattice gas, and lattice gas with energy distribution.
  • Investigation of the role of sticking coefficient and vibrational contributions in TPD analysis.
  • Development of a program for simulation and analysis of TPD data.

Main Results:

  • A new method based on equilibrium thermodynamics is presented for TPD analysis.
  • The coverage dependence of the sticking coefficient determines the order of desorption kinetics.
  • Equations are provided to directly convert peak temperatures to adsorption energies for single adsorption sites.
  • A method to extract the distribution of adsorption energies from TPD spectra is developed.

Conclusions:

  • The new thermodynamic method offers a more straightforward approach to TPD analysis compared to traditional methods.
  • The study clarifies the influence of sticking coefficients and vibrational contributions on TPD quantitative analysis.
  • The developed method and accompanying program facilitate a more accurate understanding of surface-adsorbate interactions and energy distributions.