42 research outputs found

    Hydrogen oxidation reaction on Pt in acidic media: Adsorption isotherm and activation free energies

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    We present a method for quantifying the kinetic current of the hydrogen oxidation reaction (HOR) on Pt in acidic media using the adsorption and activation free energies as the intrinsic kinetic parameters. Our approach involves deriving the HOR intermediate's adsorption isotherm based on the same dual-pathway reaction model as for the kinetic equation. Coupled with density functional theory calculations of the coverage- and site-dependent hydrogen dissociation free energies, we analyzed the adsorption isotherms for H on atop (HAtop) sites and in hollow/bridge (HH/B) sites obtained respectively from infrared spectroscopic and electrochemical measurements. Although the hydrogen dissociative adsorption energy is not site-sensitive on Pt, HAtop has an order of magnitude lower coverage and higher activity than HH/B. We attributed this distinction to their different entropies; HH/B is less accessible to water than HAtop. and the formation of a hydrogen bond is essential in the oxidative generation of H3O+. Using volcano plots, we illustrated possible ways that the exchange current may vary with the adsorption free energy and discussed the factors that contributed to the exceptionally high activity of Pt for the HOR. © 2007 American Chemical Society

    The contribution of biological sex to heat stress-mediated outcomes in growing pigs

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    Heat stress (HS) negatively impacts a variety of production parameters in growing pigs; however, the impact of biological sex on the HS response is largely unknown. To address this, 48 crossbred barrows and gilts (36.8 ± 3.7 kg BW) were individually housed and assigned to one of three constant environmental conditions: (1) thermoneutral (TN) (20.8 ± 1.6 °C; 62.0 ± 4.7% relative humidity; n = 8/sex), (2) HS (39.4 ± 0.6 °C; 33.7 ± 6.3% relative humidity) for 1 d (HS1; n = 8/sex), or (3) or for 7 d (HS7; n = 8/sex). As expected, HS increased rectal temperature (Tr) following 1 d of HS (1.0 °C; P < 0.0001) and 7 d of HS (0.9 °C; P < 0.0001). By 7 d, heat-stressed gilts were cooler than barrows (0.4 °C; P = 0.016), despite identical heating conditions. There was a main effect of sex such that barrows had higher Tr than gilts (P = 0.031). Heat-stressed pigs on d 1 had marked reductions in feed intake and BW compared to TN (P < 0.0001). One day of HS resulted in negative gain to feed (G:F) in barrows and gilts and was reduced compared to TN (P < 0.0001). Notably, following 1 d of HS, the variability of G:F was greater in gilts than in barrows. Between 1 and 7 d of HS, G:F improved in barrows and gilts and were similar to TN pigs, even though HS barrows had higher Tr than gilts over this period. Heat stress for 1 and 7 d reduced empty gastrointestinal tract weight compared to TN (P < 0.0001). Interestingly, HS7 gilts had decreased gastrointestinal tract weight compared to HS1 gilts (2.43 vs 2.72 kg; P = 0.03), whereas it was similar between HS1 and HS7 barrows. Lastly, a greater proportion of gastrointestinal contents was in the stomach of HS1 pigs compared to TN and HS7 (P < 0.05), which is suggestive of decreased gastric emptying. Overall, HS barrows maintained an elevated Tr compared to HS gilts through the duration of the experiment but also maintained similar growth and production metrics compared to gilts, despite this higher temperature

    REVIEW OF TRANSFER FUNCTION MEASUREMENTS IN THE NUCLEAR ROCKET PROGRAM USING NOISE TECHNIQUES

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