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Absorption of hydrogen at the iron-solution interface: FTIR and RT approach

Thesis/Dissertation ·
OSTI ID:6928363
An investigation of the relation of surface H to that adsorbed in the metal was carried out. The adsorption of thiourea and thiocyanate in solution on iron was also studied. The work carried out included the measurement of the coverage of iron electrodes with H as a function of potential in borate buffer solution, pH = 8.4, in the presence and absence of inhibitors, utilizing a new technique (FTIR); the determination of the hydrogen evolution reaction (HER) with H and D to obtain isotope effect; the determination of adsorption on iron as a function of potential and concentration of thiourea and thiocyanate; the determination of diffusion and solubility of H in Fe at a variety of electrode potentials in ranges relevant to corrosion. Rationalization of the overpotential relation to theta/sub H/ and C/sub H/ was obtained. A plot of C/sub H/ vs theta/sub H/ produces a straight line with slope K which was deduced from a Langmuirian approach. The presence of thiocyanate increased the K value due to a reduction in the rate of hydrogen discharge. It was also found that the majority of H is absorbed on the surface. The increase of hydrogen permeation in the presence of thiourea and thiocyanate is due to the adsorption of these additives on high energy sites leaving the low energy sites for the hydrogen discharge. The adsorption of thiourea fits a Bockris-Swinkels isotherm which represents a water displacement model. Thiourea was found to displace 3 water molecules. Thiocyanate adsorption was found to fit a Bockris-Devanathan-Muller isotherm.
Research Organization:
Texas A and M Univ., College Station (USA)
OSTI ID:
6928363
Country of Publication:
United States
Language:
English