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On the use of the Langmuir and other adsorption isotherms in corrosion inhibition
Anton Kokalj, 2023, original scientific article

Abstract: In corrosion inhibition studies, the standard adsorption Gibbs energy is often estimated via the linear regression of the Langmuir isotherm in the �∕� = 1∕� + � form, where both the intercept and the slope are estimated, although the Langmuir isotherm requires the slope of 1. Hence, �∕� = 1∕� +�� is actually used, where � is the slope. Herein, a theoretical basis for this equation is established. It is demonstrated to be an effective equation that can decently describe various adsorption models and provide relatively accurate estimates of the standard adsorption Gibbs energy, provided surface coverages are reliably determined experimentally. However, any significant deviation from the slope of 1 signals non-Langmuir adsorption due to inter-adsorbate interactions, multi-site adsorption, or surface heterogeneity. Among these three causes, only attractive inter-adsorbate interactions lead to a slope of less than 1.
Keywords: Langmuir isotherm, Flory–Huggins isotherm, Temkin isotherm, corrosion inhibition, standard adsorption free energy
Published in DiRROS: 23.04.2025; Views: 83; Downloads: 28
.pdf Full text (2,79 MB)

40.
Considering the concept of synergism in corrosion inhibition
Anton Kokalj, 2023, original scientific article

Abstract: Synergism in corrosion inhibition and how to best quantify it is explored conceptually. In the equation for the synergistic parameter, the mixture’s inhibition efficiency is evaluated against a threshold inhibition efficiency based on the performance of pure compounds. However, the choice for the threshold value is not unique. In the literature, the threshold of Aramaki–Hackerman is usually used. Herein, several other reasonable choices are developed, which are based on (i) the Langmuir adsorption model, (ii) the requirement that a mixture’s inhibition efficiency is higher than the highest inhibition efficiency of pure compounds, or (iii) that corrosion resistance in a mixture is higher than the sum of resistances in pure compounds. The presented synergistic models are also extended to multi-component mixtures.
Keywords: corrosion inhibition, synergism, Langmuir adsorption model
Published in DiRROS: 23.04.2025; Views: 91; Downloads: 29
.pdf Full text (1,65 MB)

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