Behavior of Lβ2 visible satellites in gold around L1 threshold

The Au $L{\beta }_2$ visible satellites, $L{\beta }_2^{\prime }$ and $L{\beta }_2^{″}$ were measured around the $L_1$ absorption edge using a high-resolution Johann-type spectrometer at BL15XU, SPring-8. The relative intensities of the $L{\beta }_2^{\prime }$ and $L{\beta }_2^{″}$ satellites to that of the $L{\beta }_2$ line exhibit an abrupt jump at the $L_1$ threshold. The results suggest that the origin of the $L{\beta }_2$ satellites is mainly the $L_1$–$L_3{M}_{4,5}$ Coster–Kronig transitions.     

Über die anodische oxidation von hydrazinderivaten an platin im sauren elektrolyten: Teil III. Dimethylhydrazin

As can be seen from controlled potential electrolysis the anodic oxidation of dimethyl-hydrazine in acid solutions yields two electrons per DMH molecule, giving the following overall reaction:

${(C{H}_3)}_2\stackrel{+}{N}HN{H}_2\to {(C{H}_3)}_2\stackrel{+}{N}=NH+2H^{+}+2e^{?}$

But the kinetics of the reaction is determined by a 1-electron step as the 110 mV Tafel slope shows. The reaction orders for DMH and H⁺ are z_DMH=0.54 and z_H⁺=?0.55 respectively. These results can be interpreted by the following reaction mechanism, where adsorption and desorption step are governed by the Temkin isotherm

$\begin{array}{l}{\left(C{H}_3\right)}_2\stackrel{+}{N}HN{H}_2?{\left(C{H}_3\right)}_2\stackrel{+}{N}HNH?Pt+H^{+}+e^{?}\\ {\left(C{H}_3\right)}_2\stackrel{+}{N}HNH?Pt\stackrel{r.d.s.}{\to }{\left(C{H}_3\right)}_2\stackrel{+}{N}=NH+PtH\\ PtH\to Pt+H^{+}+e^{?}\end{array}$

     

Standard molar Gibbs free energy of formation of Pb5CrO8(s), Pb2CrO5(s), and PbCrO4(s)

Standard molar Gibbs free energy of formation of ternary oxides Pb₅CrO₈(s), Pb₂CrO₅(s), and PbCrO₄(s) were determined by measuring equilibrium oxygen partial pressures over relevant phase fields using manometry and solid oxide electrolyte based emf methods and are given by: ${\mathrm{\Delta }}_f{G}_m^{°}{\text{Pb}}_5{\text{CrO}}_8(s)\pm 0.55/(\text{kJ}·{\text{mol}}^{-1})=-1809.4+0.6845(T/\text{K})(837\le T/\text{K}\le 1008)\text{,}$${\mathrm{\Delta }}_f{G}_m^{°}{\text{Pb}}_2{\text{CrO}}_5(\text{s})\pm 0.30/(\text{kJ}·{\text{mol}}^{-1})=-1161.3+0.4059(T/\text{K})(859\le T/\text{K}\le 1021)\text{,}$${\mathrm{\Delta }}_{\text{f}}{G}_m^{°}{\text{PbCrO}}_4(\text{s})\pm 0.17/(\text{kJ}·{\text{mol}}^{-1})=-909.8+0.3111(T/\text{K})(863\le T/\text{K}\le 1093)\text{,}$     

Electrochemical study on determination of diffusivity,activity and solubility of oxygen in liquid bismuth

Diffusivity of oxygen in liquid bismuth was measured by potentiostatic method and is given by$\lg (D_{\mathrm{O}}^{\mathrm{Bi}}/{\mathrm{cm}}^2·{\mathrm{s}}^{-1})(\pm 0.042)=-3.706-1377/(T{\mathrm{K}}^{-1})(804<T/\mathrm{K}<1090)\text{.}$Activityof oxygen in bismuth was determined by coulometric titrations and using the measured data standard free energy of dissolution of oxygen in liquid bismuth was derived for the reaction:$1/2{\mathrm{O}}_2(\mathrm{g})=[\mathrm{O}{]}_{\mathrm{Bi}}(\mathrm{at}\text{.}\%)$and is given by$\mathrm{\Delta }{G}_{\mathrm{O}(\mathrm{Bi})}^{\circ }/(\mathrm{J}·\mathrm{g}\text{-}\mathrm{atom}{\mathrm{O}}^{-1})(\pm 720)=-108784+20.356T{\mathrm{K}}^{-1}(753<T/\mathrm{K}<1020)\text{.}$Using the above data and Gibbs free energy of formation of Bi₂O₃ (s), solubility of oxygen in liquid bismuth was derived as a function of temperature and is given by the following expressions:$\begin{array}{cc}\hfill & \lg (S/\mathrm{at}\%\mathrm{O})(\pm 0.05)=-4476/T{\mathrm{K}}^{-1}+4.05(753<T/\mathrm{K}<988)\text{;}\hfill \\ \hfill & \lg (S/\mathrm{at}\text{.}\%\mathrm{O})(\pm 0.04)=-3786/T{\mathrm{K}}^{-1}+3.36(988<T/\mathrm{K}<1020)\text{.}\hfill \end{array}$The present data on solubility of oxygen in liquid bismuth is compared with the literature data.