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• W2050461143 abstract "The rate of adsorption of O2 upon NiO + 0, 0.01, and 1.0 mole % Li2O has been studied at constant pressure, about 10−1 mm, between −78 ° and about 400 °C. Elovich kinetics are obeyed throughout, both log (rate) vs. θ and log (t + t0) vs. θ being linear; t0 is always zero. The adsorptions obey the general equation Rate = A0Px exp (−mθ) exp (−ERT) Below the Néel point (TN), x = 0 and E is small (0–612 ± 112 kcal mole−1); above this temperature x ~ 1and E ~ 14 to 18 ± 3 kcal mole−1 while m does not change much at the transition temperature. At the higher temperatures the chemisorption is accompanied by a very much slower incorporation into the lattice, which continues for many days. Isotopic experiments revealed that substantial desorption occurs while the adsorption is proceeding. Addition of Li first decreased and then at 1.0 mole % Li2O increased the initial rate of adsorption below TN; above this temperature the main effect of Li is to increase the saturation coverage at constant pressure. In all cases the saturation coverage is minimal around 30–60 °C, increasing at both lower and higher temperatures. O2 is weakly chemisorbed in an uncharged molecular form, O2(a), below room temperature; above this increasing amounts of O2− are formed and above TN the adsorbed species is mainly O−. It is suggested that adsorption occurs mainly along the exposed boundaries of the magnetic domains; below TN the magnetostriction prevents the formation of 2 Ni3+ as nearest neighbors and so adsorption occurs as O2−, suitable sites being activated by the diffusion of P+ away from them, this being the rate-limiting process. Above TN the restriction on neighboring Ni3+ is removed and O2 molecules possessing enough kinetic energy (14–18 kcal mole−1) are chemisorbed as 2 O−." @default.
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• W2050461143 date "1966-08-01" @default.
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• W2050461143 title "Adsorption upon pure and lithium-doped nickel oxide" @default.
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• W2050461143 doi "https://doi.org/10.1016/0021-9517(66)90107-2" @default.
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