Surface oxidation and reduction of platinum electrodes: Coverage, kinetic and hysteresis studies

1968 ◽  
Vol 46 (6) ◽  
pp. 875-890 ◽  
Author(s):  
D. Gilroy ◽  
B. E. Conway

Studies on the electrochemical formation and reduction of surface oxide at platinum electrodes have been carried out with particular reference to polarization and hysteresis effects in these processes. Comparisons between the results of galvanostatic and potential sweep techniques have been made for three types of surfaces of platinum electrodes prepared by: (a) heating in hydrogen; (b) heating in a flame; and (c) electrolytically forming platinum black surfaces. The dependence of the quantity of reducible oxide formed under prior steady-state potentiostatic conditions has been related to potential and time of anodic polarization. Polarization effects in the reduction of the surface oxide have been evaluated in terms of the potential dependence of the pseudocapacitance maximum for the oxide reduction process, and a mechanism for the reduction is suggested. The relative slowness of the reduction process is important in regard to the question of the role of oxide in the kinetics of electrocatalytic oxidations at platinum anodes. Hysteresis effects in anodic formation and cathodic reduction of the oxide are discussed in terms of a totally irreversible phase transition involving the ad-layer.

CORROSION ◽  
2012 ◽  
Vol 68 (6) ◽  
pp. 507-517 ◽  
Author(s):  
K. D. Ralston ◽  
G. Williams ◽  
N. Birbilis

Prior works show that grain size can play a role in the corrosion of a metal; however, such works are nominally executed in a single electrolyte/environment at a single pH. In this work, the anodic and cathodic reaction kinetics of pure Mg specimens with grain sizes ranging from approximately 8 μm to 590 μm were compared as a function of pH in 0.1 mol dm−3 sodium chloride (NaCl) electrolytes using anodic polarization experiments and an in situ scanning vibrating electrode technique (SVET). Anodic polarization experiments showed that grain size is important in determining overall electrochemical response, but the environment dictates the form of the grain size vs. corrosion rate relationship (i.e., pH is the overall controlling factor). Consequently, the role of grain size upon corrosion cannot be fully assessed unless a variation in environment is simultaneously studied. For example, the anodic reaction, which dictates active corrosion, also dictates passivation, so the corrosion rate vs. grain size relationship has been shown to “flip” depending on pH. Further, SVET analysis of unpolarized Mg immersed in 0.1 mol dm−3 NaCl electrolyte at neutral pH showed that breakdown of passivity of cast Mg occurred after ~1 h immersion, giving filiform-like corrosion tracks. The front edges of these corrosion features were revealed as intense local anodes, while the remainder of the dark-corroded Mg surface, left behind as the anodes traversed the surface, became cathodically activated. In contrast, grain-refined Mg samples were significantly less susceptible to localized corrosion, and breakdown was not observed for immersion periods of up to 24 h.


1988 ◽  
Vol 49 (C8) ◽  
pp. C8-1711-C8-1712 ◽  
Author(s):  
S. Klahn ◽  
H. Heitmann ◽  
M. Rosenkranz ◽  
H. J. Tolle

1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.


Author(s):  
Aminata Hallimat Cissé ◽  
Sandrine Lioret ◽  
Blandine de Lauzon-Guillain ◽  
Anne Forhan ◽  
Ken K. Ong ◽  
...  

Abstract Background Early adiposity rebound (AR) has been associated with increased risk of overweight or obesity in adulthood. However, little is known about early predictors of age at AR. We aimed to study the role of perinatal factors and genetic susceptibility to obesity in the kinetics of AR. Methods Body mass index (BMI) curves were modelled by using mixed-effects cubic models, and age at AR was estimated for 1415 children of the EDEN mother–child cohort study. A combined obesity risk-allele score was calculated from genotypes for 27 variants identified by genome-wide association studies of adult BMI. Perinatal factors of interest were maternal age at delivery, parental education, parental BMI, gestational weight gain, maternal smoking during pregnancy, and newborn characteristics (sex, prematurity, and birth weight). We used a hierarchical level approach with multivariable linear regression model to investigate the association between these factors, obesity risk-allele score, and age at AR. Results A higher genetic susceptibility to obesity score was associated with an earlier age at AR. At the most distal level of the hierarchical model, maternal and paternal educational levels were positively associated with age at AR. Children born to parents with higher BMI were more likely to exhibit earlier age at AR. In addition, higher gestational weight gain was related to earlier age at AR. For children born small for gestational age, the average age at AR was 88 [±39] days lower than for children born appropriate for gestational age and 91 [±56] days lower than for children born large for gestational age. Conclusion The timing of AR seems to be an early childhood manifestation of the genetic susceptibility to adult obesity. We further identified low birth weight and gestational weight gain as novel predictors of early AR, highlighting the role of the intrauterine environment in the kinetics of adiposity.


2021 ◽  
Vol 22 (7) ◽  
pp. 3787
Author(s):  
Hussam Ibrahim ◽  
Philipp Reus ◽  
Anna Katharina Mundorf ◽  
Anna-Lena Grothoff ◽  
Valerie Rudenko ◽  
...  

Repressor protein period (PER) complexes play a central role in the molecular oscillator mechanism of the mammalian circadian clock. While the main role of nuclear PER complexes is transcriptional repression, much less is known about the functions of cytoplasmic PER complexes. We found with a biochemical screen for PER2-interacting proteins that the small GTPase regulator GTPase-activating protein and VPS9 domain-containing protein 1 (GAPVD1), which has been identified previously as a component of cytoplasmic PER complexes in mice, is also a bona fide component of human PER complexes. We show that in situ GAPVD1 is closely associated with casein kinase 1 delta (CSNK1D), a kinase that regulates PER2 levels through a phosphoswitch mechanism, and that CSNK1D regulates the phosphorylation of GAPVD1. Moreover, phosphorylation determines the kinetics of GAPVD1 degradation and is controlled by PER2 and a C-terminal autoinhibitory domain in CSNK1D, indicating that the regulation of GAPVD1 phosphorylation is a novel function of cytoplasmic PER complexes and might be part of the oscillator mechanism or an output function of the circadian clock.


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