We propose a methodological framework to quantify the relative abundance of key surface intermediates via analysis of the macroscopic intrinsic kinetic characteristics of gas-phase data. At the core of this approach is the development of analytical expressions, which link reaction orders and activation energies in macroscopic power law models to the fractional coverage of the non-observable intermediates. Through the design of an advanced parameter estimation methodology, these relationships were further exploited to develop thermodynamically consistent and mechanistic-based power law models which could capture the evolution of surface occupancy profiles along the reactor length. The developed framework was tested through in-silico water gas shift reaction case-studies; the results indicate the robustness of the approach and the mechanistic insight that can be gained from its application. The methodology proposed in this study could thus be of general value to assist in reaction mechanism analysis, identification of key surface intermediates, and reactor optimization.

中文翻译：

---

破解幂律模型的物理洞察：弥合宏观动力学和表面覆盖之间的差距


我们提出了一种方法框架，通过分析气相数据的宏观内在动力学特征来量化关键表面中间体的相对丰度。这种方法的核心是解析表达式的发展，它将宏观幂律模型中的反应级数和活化能与不可观察中间体的分数覆盖联系起来。通过设计先进的参数估计方法，这些关系被进一步利用来开发热力学一致和基于机械的幂律模型，该模型可以捕获沿反应器长度的表面占据分布的演变。所开发的框架通过计算机水煤气变换反应案例研究进行了测试；结果表明该方法的稳健性以及可以从其应用中获得的机制见解。因此，本研究提出的方法对于协助反应机理分析、关键表面中间体的识别和反应器优化具有普遍价值。