Effect of organic corrosion inhibitors on the kinetics of the cathodic hydrogen evolution reaction on steel in a sulfuric acid solution

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Abstract

The kinetics of hydrogen cathodic reduction on low-carbon steel in a sulfuric acid solution containing a mixture of quaternary ammonium salts (catamine AB) and 3-substituted 1,2,4-triazole (IFKhAN-92 inhibitor) has been studied. The main rate constants of the stages of evolution of gaseous hydrogen and the permetion of hydrogen atoms into the metal are determined. It is shown that these substances reduce the reaction rate of the discharge of H+ ions, change the ratio between the concentrations of H atoms on the surface and in the phase of the metal, and, as a result, reduce the amount of hydrogen absorbed by steel. The most effective inhibitor of corrosion and hydrogenation of steel is IFKhAN-92, due to the formation of a polymolecular protective layer of the inhibitor on the metal surface. The data of X-ray photoelectron spectroscopy of the steel surface show that the protective layer has a thickness of no more than 4 nm and consists of IFKhAN-92 molecules associated with the steel surface by chemical interaction, and inside the layer by physical interaction.

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About the authors

Ya. G. Avdeev

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Author for correspondence.
Email: avdeevavdeev@mail.ru
Russian Federation, Moscow

T. A. Nenasheva

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Email: avdeevavdeev@mail.ru
Russian Federation, Moscow

A. Y. Luchkin

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Email: avdeevavdeev@mail.ru
Russian Federation, Moscow

A. I. Marshakov

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Email: avdeevavdeev@mail.ru
Russian Federation, Moscow

Yu. I. Kuznetsov

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Email: avdeevavdeev@mail.ru
Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Electrochemical Devanathan–Stakhursky cell: 1 - working electrode (membrane); 2 - Teflon holder; 3 - working part of the cell; 3 ′ – diffusion part of the cell; 4, 4 ′ - auxiliary electrode cell; 5, 5 ′ – auxiliary electrode; 6, 6 ′ - electrolytic key; 7, 7 ′ - reference electrode; 8, 8 ′ - tap for draining the solution; 9, 9 ′ - injection of solution into the cell; 10—argon input into the cell; 11 - water seal.

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3. Fig. 2. Cathode polarization curves (a) and dependences of the rate of hydrogen penetration into iron on the potential of a steel membrane (b) in 2 M H2SO4 containing catamine AB.

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4. Fig. 3. Cathode polarization curves (a) and dependences of the rate of hydrogen penetration into iron on the potential of a steel membrane (b) in 2 M H2SO4 containing IFKhAN-92.

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5. Fig. 4. Dependence of the current of hydrogen penetration through the membrane on the rate of its chemical recombination in 2 M H2SO4 containing catamine AB and IFKhAN-92.

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6. Fig. 5. Dependence of the function f = ic exp (αFE/RT) on the current of hydrogen penetration through a membrane in 2 M H2SO4 containing catamine AB and IFKhAN-92.

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7. Fig. 6. Equivalent electrical circuit and Nyquist diagrams of a steel electrode (0.64 cm2, E = –0.30 V) 2 M H2SO4, taken after introducing 0.05 mM IFKHAN-92 into a solution with different exposure times.

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8. Fig. 7. Adsorption isotherm of catamine AB () and IFKHAN-92 (•) on low-carbon steel (E = –0.30 V) from 2 M H2SO4.

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9. Fig. 8. Anodic and cathodic polarization curves on spring steel at t = 25 °C in 2 M H2SO4 without and in the presence of 5 mM catamine AB and IFKHAN-92.

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10. Fig. 9. Standard XPS spectrum of Fe(2p3/2) electrons (spin orbit splitting - doublet) of the surface of low-carbon steel after preliminary adsorption of IR (2 M H2SO4 + 5 mM IFKhAN-92, 25 °C, 24 h).

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11. Fig. 10. XPS spectra of O(1s) electrons on the surface of low-carbon steel after preliminary adsorption of IR (2 M H2SO4 + 5 mM IFKhAN-92, 25 °C, 24 h).

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12. Fig. 11. XPS spectra of N(1s) electrons on the surface of low-carbon steel, after preliminary adsorption of IR (2 M H2SO4 + 5 mM IFKhAN-92, 25 °C, 24 h) followed by washing in an ultrasonic bath.

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