In the absence of a bulk diffusion effect, it is shown for the first time that the impedance spectra for the chlorine evolution reaction on a rotating thin ring electrode comprise three consecutive semicircles in the capacitive half of the complex plane. The first (highest frequency) semicircle is due to the charge-transfer resistance for chloride discharge and the simultaneous chlorine adsorption coupled to the double-layer capacitance. The second semicircle (around 5 Hz) is due to the adsorption and desorption of a chlorine intermediate. The third (lowest frequency, around 0.5 Hz) semicircle is due to the relaxation of surface oxygen species. The impedance data allow the steps of the overall reaction to be examined individually. On a Pt surface the rate of chloride discharge and simultaneous chlorine adsorption (the admittance of the first semicircle) is first order with respect to chloride concentration and has a potential-dependence close to 58 mV/decade. The rate of the adsorption and desorption process (the admittance of the second semicircle) is second order with respect to chloride concentration, and has a potential dependence close to 30 mV/decade. The time constant for the adsorption/desorption processes is ca 20 ms, independent of electrode potential in the range studied. These features are consistent with a mechanism in which a faster discharge reaction (Cl− Clad + e) is followed by a slower surface combination reaction (2Clad → Cl2), but inconsistent with mechanisms in which ion + atom desorption is predominant, the initial chloride discharge is slow, or a unipositively charged chlorine species is involved. 相似文献
The samples of the series Co1+ySnyFe2- 2y- xCrxO4 ferrites with x = 0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and y = 0.05, were prepared by the usual double sintering ceramic technique. The single- phase spinel structure of the samples was confirmed by using X- ray diffractometry technique. The lattice parameter ’a’ with an accuracy of ± 0.002 Å were determined using Bragg peaks of XRD pattern. The lattice parameter ’a’ decreases with concentration, x, which is due to the difference in the ionic radii of Cr3+ and Fe3+ ions. The X- ray intensity calculations were carried out in order to determine the possible cation distribution amongst tetrahedral (A) and octahedral [B] sites. The X- ray intensity calculations show Cr3+ ions occupying B site. The saturation magnetization, σs, and magneton number, nB (the saturation magnetization per formula unit), measured at 300 K determined from high field hysteresis loop technique decrease with increase in concentration, x, suggesting a decrease in ferrimagnetic behaviour. Thermal variation of low field a.c. susceptibility measurements from room temperature to about 800 K exhibits almost normal ferrimagnetic behaviour and the Curie temperature, TC determined from a.c. susceptibility data decreases with increase in x.
Data on adolescents' after-school experiences and their susceptibility to peer pressure were derived from surveys administered to a heterogeneous sample of 865 adolescents in Grades 5–9. Consistent with the findings of previous studies, the results show that Ss who reported home after school were not significantly different from those who were supervised by their parents at home during after-school hours. However, when a 2nd sample of latchkey children (n?=?594) was studied to include greater variation in after-school experiences, Ss who were more removed from adult supervision were found to be more susceptible to peer pressure to engage in antisocial activity. Ss who were home alone were less susceptible to peer pressure than are those who were at a friend's house after school, and those who were at a friend's house, in turn, were less susceptible than were those who describe themselves as "hanging out." Moreover, latchkey Ss whose parents knew their whereabouts and those who had been raised authoritatively were less susceptible to peer influence than were their peers, even if their afternoons were spent in contexts in which adult supervision was lax and susceptibility to peer pressure was generally high. (17 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved) 相似文献
The measurements of ac conductivity [σm(ω)], dielectric constant [?′(ω)] and loss [?″(ω)] have been performed on solution grown (thickness ∼85 μm) and uniaxially stretched (thickness ∼25, 45 and 80 μm) films of poly(vinylidene fluoride) (PVDF) in the frequency range 0.1 kHz-10 MHz and in the temperature range 77-400 K. The σm(ω) can be described by the relation σ(ω) = Aωs, where s is close to unity and decreases with increase in temperature. Three relaxations, observed in the present investigation, have been designated as the αc-, the αa- and the β-relaxations appearing from high temperature side to the low temperature side. The αc-relaxation could not be observed in the case of uniaxially stretched poly(vinylidene fluoride) films. The αc- and αa-relaxations are associated with the molecular motions in the crystalline regions and micro-Brownian motion in the amorphous regions of the main polymer chain, respectively, whereas the β-relaxation is attributed to the rotation of side group dipoles or to the local oscillations of the frozen main polymer chain. 相似文献
The oxidative absorption of hydrogen sulfide (H2S) into a solution of ferric chelate of trans-1,2- diaminocyclohexanetetraacetate (CDTA) was studied in a counter-current laboratory column randomly packed with 15 mm plastic Ralu rings. The present investigation takes concern about the Kraft pulping situation where dilute H2S concentrations are omnipresent in large-volume gas effluents. A fractional two-level factorial approach was instigated to determine the significance of six operating variables, namely the solution's alkalinity (pH; 8.5-10.5), the liquid mass flow rate (L;1.73-), the solution's ionic strength (IC;0.01-), the gas mass flow rate (G;0.19-), the inlet H2S concentration (CH2S,0;70-430 ppm) and the initial ferric CDTA concentration (CFe,0;100 -). Initially, a Plackett-Burman design matrix of seven duplicated experiments revealed that pH is the leading factor controlling the H2S conversion rate while the ionic strength and ferric CDTA concentration effects remained negligible within the factorial domain. Surface response analysis based on 11 duplicated factorial experiments plus 10 central composite trials revealed that the H2S conversion significantly increases with liquid flow rate but decreases with growing H2S load up. Further examination about the influence of ferric CDTA on H2S absorption rate was set up over a broader concentration range (CFe,0;0- at pH of 9.5 and 10.5. It showed good potential at as H2S conversion increased by a significant 25% for both pH values in comparison to pure alkaline solutions containing no ferric CDTA. 相似文献