Comparative Rates of the Electrolytic Evolution of Hydrogen and Deuterium on Iron, Tungsten and Platinum

Bockris, J. O'm.; Koch, D. F. A.

doi:10.1021/j100828a007

Cited by 86 publications

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“…The low slope value corresponds to the Volmer-Tafel mechanism and the high slope value corresponds to the Heyrovsky-Tafel mechanism. The Tafel slopes of DER, too, could be divided into two other result [30]. The present values of the exchange current density are larger than general values [28][29][30].…”

Section: Her and Dermentioning

confidence: 60%

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Study of Deuterium Isotope Separation by PEFC

Shibuya

Matsushima

Ueda

2016

J. Electrochem. Soc.

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Hydrogen evolution and oxidation reactions were studied on a polycrystalline platinum electrode in 0.05 M D 2 SO 4 solution at 298 K by using a rotating disk electrode, focusing on the kinetic isotope effect on reactivity. The polarization measurements in the evolution reaction regime, on the one hand, revealed two Tafel regions: at low overpotentials close to the equilibrium potential, the Tafel slope was 0.039 V dec -1 , suggesting a Volmer-Tafel mechanism; and at potentials around 0.05 V or lower, a slope of 0.168 V dec -1 indicated that a transition to a Heyrovsky-Tafel mechanism occurred.In the oxidation reaction regime, on the other hand, a single Tafel slope of 0.055 V dec -1 was observed at potentials of 0.08 V or lower. Comparing between the deuterium and protium data for the kinetic factors supported the presence of an isotope effect, whereby the deuterium was more easily dissociated on the platinum electrode. The present kinetic result supported the deuterium separation of polymer electrolyte fuel cell (PEFC) in which the mixture gases of H 2 and D 2 were purged. The deuterium separation factor increased with increasing in the hydrogen utilization. This suggests a new isotope separation technique and also provides useful data for fuel cells.

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Section: Her and Dermentioning

confidence: 60%

“…However, there are a few experimental studies on the kinetic factors of the deuterium evolution reaction (DER) [29]. Previously, Bockris et al reported that the Tafel slope of DER was 0.026 V dec -1 , which was similar to that of HER (0.029 V dec -1 ), whereas the exchange current of DER was much smaller than that of HER [30].…”

Section: Introductionmentioning

confidence: 99%

Study of Deuterium Isotope Separation by PEFC

Shibuya

Matsushima

Ueda

2016

J. Electrochem. Soc.

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“…Many previous studies of hydrogen evolution reaction on pure iron have shown that the Volmer reaction is appropriate as the ratedetermining step. 25,[27][28][29] Thus, hydrogen evolution reactions on pure iron and cast iron are found to be the same.…”

Section: Mechanism Of Hydrogen Evolution Reaction On Cast Ironmentioning

confidence: 70%

Hydrogen Evolution Reaction on Spheroidal Graphite Cast Iron with Different Graphite Areas in Sulfuric Acid Solutions

et al. 2014

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The rate equation of hydrogen evolution reaction on spheroidal graphite cast iron which has different areas of graphite particles has been studied in sulfuric acid solutions at 298 K. The cathodic Tafel slope of −0.125 V/decade and the reaction order with respect to the activity of hydrogen ion of 1 are obtained by linear potential sweep technique. The cathodic current density due to hydrogen evolution reaction does not depend on the area of graphite particles. There is no difference in hydrogen evolution reaction mechanism between pure iron and spheroidal graphite cast iron.

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“…Three rate determining mechanisms of the hydrogen evolution process has been proposed including the slow discharge mechanism, the electro-chemical desorption mechanism, and the atom recombination mechanism. 26,27 Regardless of the exact mechanism, the kinetic ratio of hydrogen and deuterium evolution is dependent on the difference in the heat of activation between proton and deuterium discharge, the difference in the heats of adsorption between hydrogen and deuterium, as well as the surface coverage of the adsorbed reactants at the electrode. 26,27 Theoretical calculation indicated that the isotopic ratio of exchange current density for hydrogen and deuterium evolution on metals varies between 2 and 27.…”

Section: Resultsmentioning

confidence: 99%

“…For instance, the deuterium evolution kinetics are more sluggish than the hydrogen evolution. [26][27][28][29] This kinetic isotope effect has been used in electrolytic separation of heavy water from natural water. In other studies, heavy water was reported to be a stronger oxidizer than regular water in acidic media.…”

mentioning

confidence: 99%

Polarized Neutron Reflectometry of Metal Consumption and Passive Film Growth on Nickel Exposed to an Alkaline Deuterium Oxide (D₂O) Solution

Fritzsche

Burton

et al. 2017

J. Electrochem. Soc.

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Electrochemical behavior of Ni in an alkaline heavy water electrolyte was studied using cyclic voltammetry and polarized neutron reflectometry. Delays in the hydrogen and oxygen evolution reactions on Ni electrodes and slower kinetics of the reactions in heavy water compared to light water were observed. However, in both 0.01 mol/L NaOH light and heavy water solutions, Ni oxidation and passive film formation occurred at the same potential with similar passive current densities indicating a minor isotope effect of deuterium on passive film formation and growth. Polarized neutron reflectometry detected a passive film growth coefficient of 11.5 ± 1.1 Å/V. The Ni consumption coefficient was determined to be 7.3 ± 1.5 Å/V. Ni oxidation and passive film growth occurred mostly during the transient period after the applied potential increase but was negligible at the steady state. The electric field strength across the passive film was 8 × 10 6 V/cm. The Pilling-Bedworth ratio of the passive film during potentiostatic growth was close to the value of NiO grown on bulk Ni. This work demonstrated the capability of neutron reflectometry in the study of passive films on metals and alloys.

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Comparative Rates of the Electrolytic Evolution of Hydrogen and Deuterium on Iron, Tungsten and Platinum

Cited by 86 publications

References 0 publications

Study of Deuterium Isotope Separation by PEFC

Study of Deuterium Isotope Separation by PEFC

Hydrogen Evolution Reaction on Spheroidal Graphite Cast Iron with Different Graphite Areas in Sulfuric Acid Solutions

Polarized Neutron Reflectometry of Metal Consumption and Passive Film Growth on Nickel Exposed to an Alkaline Deuterium Oxide (D₂O) Solution

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Comparative Rates of the Electrolytic Evolution of Hydrogen and Deuterium on Iron, Tungsten and Platinum

Cited by 86 publications

References 0 publications

Study of Deuterium Isotope Separation by PEFC

Study of Deuterium Isotope Separation by PEFC

Hydrogen Evolution Reaction on Spheroidal Graphite Cast Iron with Different Graphite Areas in Sulfuric Acid Solutions

Polarized Neutron Reflectometry of Metal Consumption and Passive Film Growth on Nickel Exposed to an Alkaline Deuterium Oxide (D2O) Solution

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Polarized Neutron Reflectometry of Metal Consumption and Passive Film Growth on Nickel Exposed to an Alkaline Deuterium Oxide (D₂O) Solution