The Law of Parsimony and the Negative Charge of the Bubbles

• Published in: Coatings (Basel) Vol. 10; no. 10; p. 1003
• Main Authors: Karakashev, Stoyan I., Grozev, Nikolay A.
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 01.10.2020
• Subjects: Adsorption; Bubbles; Carbon dioxide; Experiments; Gibbs free energy; Interfaces; Mathematical analysis; Simulation; Surface water; Surfactants
• ISSN: 2079-6412; 2079-6412
• DOI: 10.3390/coatings10101003

Why the bubbles are negatively charged? This is almost 100 years old question, which many scientists have striven and still are striving to answer using the latest developments of the MD simulations and various physical analytical methods. We scrutinize with this paper the basic literature on this topic and conduct our own analysis. Following the philosophical law of parsimony: “Entities should not be multiplied without necessity”, we assume that the simplest explanation is the right one. It is well known that the negative change of the Gibbs free energy is a solid criterion for spontaneous process. Hence, we calculated the energies of adsorption of OH−, H3O+ and HCO3− ions on the air/water interface using the latest theoretical developments on the dispersion interaction of inorganic ions with the air/water interface. Thus, we established that the adsorption of OH− and HCO3− ions is energetically favorable, while the adsorption of H3O+ is energetically unfavorable. Moreover, we calculated the change of the entropy of these ions upon their transfer from the bulk to the air/water interface. Using the well-known formula ΔG = ΔH − TΔS, we established that the adsorption of OH− and HCO3− ions on the air/water interface decreases their Gibbs free energy. On the contrary, the adsorption of H3O+ ions on the air/water interface increases their Gibbs free energy. Thus, we established that both OH− and HCO3− ions adsorb on the air/water interface, while the H3O+ ions are repelled by the latter. Therefore, electrical double layer (EDL) is formed at the surface of the bubble–negatively charged adsorption layer of OH− and HCO3− ions and positively charged diffuse layer of H3O+ ions.