The determination of the standard Gibbs energies of ion transfer between water and heavy water by using the three-phase electrode approach

• Published in: Electrochemistry communications Vol. 6; no. 2; pp. 215 - 218
• Main Authors: Gulaboski, Rubin, Caban, Karolina, Stojek, Zbigniew, Scholz, Fritz
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01-02-2004; Amsterdam Elsevier Science; New York, NY
• Subjects: Chemistry; Decamethylferrocene; Exact sciences and technology; Gas-liquid interface and liquid-liquid interface; General and physical chemistry; Heavy water; Iron(III) tetraphenyl porphyrine; Standard Gibbs energy of ion transfer; Surface physical chemistry; Three-phase electrode; Iron(III) tetraphenyl porphyrine; Heavy water; Standard Gibbs energy of ion transfer; Three-phase electrode; Decamethylferrocene; Electrochemical potential; Gibbs free energy; Iron Complexes; Ion transfer; Organic ligand; Transition metal Complexes; Experimental study; Transport process; Iron Organic compounds; Organic solvent; Liquid liquid interface; Metalloporphyrin; Physicochemical properties
• ISSN: 1388-2481; 1873-1902
• DOI: 10.1016/j.elecom.2003.12.001

For the first time, the standard Gibbs energies of transfer of anions and cations across the nitrobenzene|heavy water interface are reported as measured by an electrochemical technique. The data have been obtained with the help of three-phase electrodes consisting of a nitrobenzene droplet that contains an electroactive compound (either decamethylferrocene to transfer anions or iron(III) tetraphenyl porphyrin chloride to transfer cations), a graphite electrode on the surface of which the droplet is attached, and a solution of the salts with the transferable ions in heavy water. The difference between these Gibbs energies of transfer and those of transfer between light water and nitrobenzene allows calculating the Gibbs energies of transfer between light water and heavy water. The latter vary in the interval from −0.50 to +0.50 kJ/mol with confidence intervals ranging from ±0.054 to ±0.117 kJ/mol.