Inhibiting Action of Substituted Phenols Sergey M. Beloglazov, and Georgij S. Beloglazov Kaliningrad University, Russia against Corrosion of Al in Media with Bacterial Sulphate Reduction S7FP146. 1/20 234n4n 5 pH 6Eh6Eh 7K7K 8 Z= 9 r/c Al q Quit14 r/ q 15 r/c [ref] 20 bk.p

1. Formulae of Biocides Studied S7FP146. 2/20 OH NH 2 etc.: F1 F2 F3 F4 F5F6 OUTLINE / SCOPE: 1.Class of Biocides Studied 2.Experimental Results (ER) 3.Quantum Chemical Results (QCR) 4.Comparison of QCR with ER 5.Summary, Conclusions, References ref. titles

2. EXPERIMENTAL Results of Electrochemical Measurements 2.2. pH (time), 2.3. E h (time), 2.4. corrosion rate. S7FP146. 3/ Results of bacterial population count

S7FP146. 4/ Experimental Results exposure time, days SRB cells number n, 10 7 /mL Reference (without additives) F2, 10 mMol/L F1, 1 mMol/L F1, 10 mMol/L 2.1 Cells growth / time

S7FP146. 5/ Experimental Results (continued) exposure time, days pH Reference (without additives) F2, 10 mMol/L F1, 10 mMol/L pH / time

S7FP146. 6/ Experimental Results (continued) exposure time, days -E h, mV 700 Reference (without additives) F1, 10 mMol/L F1, 1mMol/L E h / time F4, 1mMol/L

S7FP146. 7/ Experimental Results (continued) inhibitor concentration, mMol/L Corrosion rate K, g · (m -2 · days -1 ) 0,25 Reference (without additives) F1 F2 0,15 0,05 0, Corrosion rate / c

S7FP146. 8/20 DEFINITION of anti-corrosion efficiency of organic ADDITIVES Z % = {( m o - m ) / m o } · 100% m o – mass loss by specimen due to corrosion in the same media and under the same condition as m but without adding any inhibitor m– mass loss by specimen due to corrosion at the presence of an inhibitor;

S7FP146. 9/20 2. Experimentally Measured Efficiencies of F1…F6 against Corrosion (Z), % ______________________________________________________ Ref. titlesConcentration of biocydes of biocidesin corrosion media, mMol/L studied F F F F F F

3. THEORETICAL Quantum Chemical Modeling: 3.1 Energies of Boundary Molecular Orbitals (HOMO, LUMO) of Isolated Molecules of Organic Inhibitors studied 3.2 Charge distribution in Inhibitor Molecules: isolated (populations, dipole moment ) adsorbed on model surface (CLUSTER) S7FP /20

S7FP /20 3. Quantum Chemical Results (isolated molecule) 123, D Anti- corrosion efficy Z, % (10 mMol/L) QCR (dipole moments of isolated molecules) ER F3 F6 F4 F2 F5 F1 r=-61%

S7FP /20 3. CLUSTER approach OH Al 12

S7FP /20 3. CLUSTER approach (continued) OH q 0 (C 1 ) q 0 (C 2 ) q 0 (O 1 ) q o (O 2 ) q* (O 1 ) q*(C 1 ) q*(C 2 ) q* (O 2 ) q ad = q ad (i) = {q*(i) - q 0 (i)} = q*(i) - q 0 (i) = - q*(Al) Al 12 OHOH OHOH

S7FP /20 4. Comparison of Quantum Chemical Data with Experiment ,5 q ad, |e| Anti- corrosion efficy Z, % (10 mMol/L) QCR (sum q ad of charges on atoms obtained due to adsorption) ER F3 F6 F4 F2 F5 F1 r=73%

S7FP /20 4. Comparison of Quantum Chemical Data with Experiment (contd) Method Pair correlation coefficients r q[Al 12 ],Z)

S7FP /20 3. CLUSTER approach (Al 2 O 3 ) OH q 0 (C 1 ) q 0 (C 2 ) q 0 (O 1 ) q o (O 2 ) q* (O 1 ) q*(C 1 ) q*(C 2 ) q* (O 2 ) q ad = q ad (i) = {q*(i) - q 0 (i)} = q*(i) - q 0 (i) = - q*(Al) Al 2 O 3 OHOH OHOH

S7FP /20 5. SUMMARY and CONCLUSIONS Bactericide action ( namely, delaying bacterial metabolism and reproduction ) of studied additives appear in decreasing the concentration of bacterial cells in the corrosive media under studied conditions The phenols {F1 … F6} studied can be satisfactory inhibitors of Al in aqueous salted media, showing inhibitive efficiencies up to 70%. The obtained concentration dependencies of corrosion rates are different for each additive Numerous properties of corrosion media are sharply changed at addition of organic bactericides, such as pH rate and redox potential E h There are certain structure-dependant parameters of the inhibitors (dipole moment as charge/geometry combination, change of atomic charges on adsorption on metal etc.) that correspond to their inhibitive efficiencies

REFERENCES G.S. Beloglazov, S.M. Beloglazov, and O. D. Gladysh. Quantum Chemical Study of Corrosion Inhibitive Action of Organic Substances // Progress in the Understanding and Prevention of Corrosion: Proc. / 10th European Congress. Barcelona p G.S. Beloglazov, S.M. Beloglazov, and S. Uss. // Progress in the Understanding and Prevention of Corrosion: Proc. / 10th European Congress. Barcelona S. M. Beloglazov and G. S. Beloglazov. Correlation of Quantum Chemical Study of Organic Compounds with their Corrosion and Hydrogen Absorption Efficiency, in: Eurocorrosion-94: Conference Papers. Bournemouth Vol.3, p S. M. Beloglazov, A. A. Myamina, and G. S. Beloglazov. Corrosion and Hydrogen Absorption Inhibitors with Biocyde Action Against Sulphate Reducing Bacteria, in: IX Int. Congress on Marine Corrosion and Fouling / Abstracts. Portsmouth G.S. Beloglazov, A.A. Myamina, S.M. Beloglazov. Understanding Mechanisms of Inhibiting Action of N-containing Organic Compounds on Corrosion and Hydrogen Absorption of Steel using Quantum Chemical Computations // EUROCORR Nice, France / Abstracts, p. 39. Gaussian 94, Revision E3 / M. J. Frisch, G. W. Trucks e. a. Gaussian. Inc, Pittsburgh PA S7FP147 ( , 13:30 POSTER): G.S. Beloglazov, M.V. Gryaznova, and S.M. Beloglazov. Quantum chemical study of pyrazoline derivatives as inhibitors of hydrogenation and SRB-induced corrosion of steel // 55 th ISE Annual Meeting of ISE. Thessaloniki, Greece / Abstracts, Vol. 2, p S7FP /20

End of Presentation Thanks for Your Attention! S7FP /2019/ n4n 5 pH 6Eh6Eh 7K7K 8 Z= 9 r/c Al q Quit Review: MS Office MS PowerPoint presentation prepared by Georgij S. Beloglazov 14 r/ q 15 r/c 20 bk.p

ELECTROCHEMICAL HYDROGEN AND METALS: BEHAVIOUR, EMBRITTLEMENT PREVENTION - monograph (in Russian) by Professor Sergei M. BELOGLAZOV, Kaliningrad university The book (321 p., 130 drawings/figures, 23 tables, 526 references) deals with the problem of cathodically discharged hydrogen, cathode protection in sea water and by electroplating processes. The original proposed method (step-stripping technique) for determination of hydrogen concentration profile in bulk steel (stepwise anodic dissolution of metal and stepped hydrogen analysis), is described. Theoretical & experimental results on hydrogen diffusion and absorption processes in steel, Pt, Pd, Ni, and Nb are reported and discussed. It is shown that experimental results on hydrogen embrittlement due to electrochemical hydrogen can be explained within the framework of interaction between sub-surface defects and the absorbed hydrogen. Hydrogen-rich sub-surface formation in cathode treated steel or steel under corrosion is analyzed, together with the opportunity of preventing such metal deterioration by electrochemical processes. Such opportunity is based on successful use of certain organic substances as additives to a number of industrial baths for electrodepositing Zn, Cd, Ni, Cr, Sn, Cu and their alloys. S7FP /20