Stable-isotope dilution activation analysis,and determination of Ca,Zn and Ce by means of photon activation

As a new method, stable-isotope dilution activation analysis has been developed. When an element consists of at least two stable isotopes which are converted easily to the radioactive nuclides through nuclear reactions, the total amount of the element (xg) can be determined by irradiating simultaneously the duplicated sample containing small amounts of either enriched isotope (y g), and by using the following equation. $${{x = y\left( {{M \mathord{\left/ {\vphantom {M {M*}}} \right. \kern-\nulldelimiterspace} {M*}}} \right)\left[ {\left( {{{R*} \mathord{\left/ {\vphantom {{R*} R}} \right. \kern-\nulldelimiterspace} R}} \right)\left( {{{\theta _2^* } \mathord{\left/ {\vphantom {{\theta _2^* } {\theta _2 }}} \right. \kern-\nulldelimiterspace} {\theta _2 }}} \right) - \left( {{{\theta _1^* } \mathord{\left/ {\vphantom {{\theta _1^* } {\theta _1 }}} \right. \kern-\nulldelimiterspace} {\theta _1 }}} \right)} \right]} \mathord{\left/ {\vphantom {{x = y\left( {{M \mathord{\left/ {\vphantom {M {M*}}} \right. \kern-\nulldelimiterspace} {M*}}} \right)\left[ {\left( {{{R*} \mathord{\left/ {\vphantom {{R*} R}} \right. \kern-\nulldelimiterspace} R}} \right)\left( {{{\theta _2^* } \mathord{\left/ {\vphantom {{\theta _2^* } {\theta _2 }}} \right. \kern-\nulldelimiterspace} {\theta _2 }}} \right) - \left( {{{\theta _1^* } \mathord{\left/ {\vphantom {{\theta _1^* } {\theta _1 }}} \right. \kern-\nulldelimiterspace} {\theta _1 }}} \right)} \right]} {\left[ {1 - \left( {{{R*} \mathord{\left/ {\vphantom {{R*} R}} \right. \kern-\nulldelimiterspace} R}} \right)} \right]}}} \right. \kern-\nulldelimiterspace} {\left[ {1 - \left( {{{R*} \mathord{\left/ {\vphantom {{R*} R}} \right. \kern-\nulldelimiterspace} R}} \right)} \right]}}$$ Where M and M^* are atomic weights of the element to be determined and the enriched isotope used as a spike,θ ₁ andθ ₂ are natural abundances of two stable isotopes in the element,θ ₁ ^* andθ ₂ ^* are isotopic compositions of the above isotopes in the enriched isotope, and R and R^* are counting ratios of gamma-rays emitted by two radionuclides produced in the sample and the isotopic mixture. Neither calibration standard nor correction of irradiation conditions are necessary for this method. Usefulness of the present method was verified by photon activations of Ca, Zn and Ce using isotopically enriched⁴⁸ca,⁶⁸Zn and¹⁴²Ce.     

Effect of long-chain branching on the relation between steady-flow and dynamic viscosity of polyethylene melts

The steady-state viscosity η, the dynamic viscosity η′, and the storage modulus G′ of several high-density and low-density polyethylene melts were investigated by using the Instron rheometer and the Weissenberg rheogoniometer. The theoretical relation between the two viscosities as proposed earlier is:\documentclass{article}\pagestyle{empty}\begin{document}$ \eta \left( {\dot \gamma } \right){\rm } = {\rm }\int {H\left( {\ln {\rm }\tau } \right)} {\rm }h\left( \theta \right)g\left( \theta \right)^{{\raise0.7ex\hbox{$3$} \!\mathord{\left/ {\vphantom {3 2}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{$2$}}} \tau {\rm }d{\rm }\ln {\rm }\tau $\end{document}, where \documentclass{article}\pagestyle{empty}\begin{document}$ \theta {\rm } = {\rm }{{\dot \gamma \tau } \mathord{\left/ {\vphantom {{\dot \gamma \tau } 2}} \right. \kern-\nulldelimiterspace} 2} $\end{document}; \documentclass{article}\pagestyle{empty}\begin{document}$ {\dot \gamma } $\end{document} is the shear rate, H is the relaxation spectrum, τ is the relaxation time, \documentclass{article}\pagestyle{empty}\begin{document}$ g\left( \theta \right){\rm } = {\rm }\left( {{2 \mathord{\left/ {\vphantom {2 \pi }} \right. \kern-\nulldelimiterspace} \pi }} \right)\left[ {\cot ^{ - 1} \theta {\rm } + {\rm }{\theta \mathord{\left/ {\vphantom {\theta {\left( {1 + \theta ^2 } \right)}}} \right. \kern-\nulldelimiterspace} {\left( {1 + \theta ^2 } \right)}}} \right] $\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$ h\left( \theta \right){\rm } = {\rm }\left( {{2 \mathord{\left/ {\vphantom {2 \pi }} \right. \kern-\nulldelimiterspace} \pi }} \right)\left[ {\cot ^{ - 1} \theta {\rm } + {\rm }{{\theta \left( {1{\rm } - {\rm }\theta ^2 } \right)} \mathord{\left/ {\vphantom {{\theta \left( {1{\rm } - {\rm }\theta ^2 } \right)} {\left( {1{\rm } + {\rm }\theta ^2 } \right)^2 }}} \right. \kern-\nulldelimiterspace} {\left( {1{\rm } + {\rm }\theta ^2 } \right)^2 }}} \right] $\end{document}. Good agreement between the experimental and calculated values was obtained, without any coordinate shift, for high-density polyethylenes as well as for a low density sample with low n_w, the weight-average number of branch points per molecule. The correlation, however, was poor with low-density samples with large values of the long-chain branching index n_w. This lack of coordination can be related to n_w. The empirical relation of Cox and Merz failed in a similar way.     

Thermodynamic properties of the ternary oxides in the Eu–Ru–O system by using solid-state electrochemical cells

The Gibbs free energies of formation of Eu₃RuO₇(s) and Eu₂Ru₂O₇(s) have been determined using solid-state electrochemical technique employing oxide ion conducting electrolyte. The reversible electromotive force (e.m.f.) of the following solid-state electrochemical cells have been measured:

Über Osmiumbromide

On Osmiumbromides OsBr₄ was obtained by reaction of OsCl₄ with bromine in a closed system at 330°C and 120 bar Br₂ pressure. The compound crystallizes orthorhombic (a = 633.99(18) pm; b = 1 210.92(16) pm; c = 1 461.5(10) pm; Z = 8; space group Pbca) in a TcCl₄ type structure. OsBr₆ octahedra are connected by two common edges to \documentclass{article}\pagestyle{empty}\begin{document}${}_\infty ^1 \left[ {{\rm OsBr}_{{{\rm 2} \mathord{\left/ {\vphantom {{\rm 2} 1}} \right. \kern-\nulldelimiterspace} 1}} {\rm Br}_{{{\rm 4} \mathord{\left/ {\vphantom {{\rm 4} 2}} \right. \kern-\nulldelimiterspace} 2}} } \right]$\end{document} chains with a cis arrangement of the two non-bridging Br atoms. Mixed crystals OsBr_xCl_4?x(0 < x < 2.3) with CsCl₄ type structure are formed by reactions at lower Br₂ pressure up to 12 bar. They are built up from chains consisting of edge-sharing octahedra. The terminal atoms have a trans arrangement. Attempts to synthesize single crystals of OsBr₃ by decomposition of OsBr₄ resulted in formation of three different phases OsBr_x (3 < x < 4).     

Improvement of the electrochemical properties of “as-grown” boron-doped polycrystalline diamond electrodes deposited on tungsten wires using ethanol

The electrochemical properties of boron-doped diamond (BDD) polycrystalline films grown on tungsten wire substrates using ethanol as a precursor are described. The results obtained show that the use of ethanol improves the electrochemistry properties of “as-grown” BDD, as it minimizes the graphitic phase upon the surface of BDD, during the growth process. The BDD electrodes were characterized by Raman spectroscopy, scanning electronic microscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The boron-doping levels of the films were estimated to be ∼10²⁰ B/cm³. The electrochemical behavior was evaluated using the and redox couples and dopamine. Apparent heterogeneous electro-transfer rate constants were determined for these redox systems using the CV and EIS techniques. values in the range of 0.01–0.1 cm s⁻¹ were observed for the and redox couples, while in the special case of dopamine, a lower value of 10⁻⁵ cm s⁻¹ was found. The obtained results showed that the use of CH₃CH₂OH (ethanol) as a carbon source constitutes a promising alternative for manufacturing BDD electrodes for electroanalytical applications.     

Photoelectrode characteristics of an organic bilayer in water phase containing a redox molecule

We have recently reported that the organic bilayer of 3,4,9,10-perylenetetracarboxyl-bisbenzimidazole (PTCBI, n-type semiconductor) and 29H,31H-phthalocyanine (H₂Pc, p-type semiconductor), which is a part of a photovoltaic cell, acts as a photoanode in the water phase (Abe et al., ChemPhysChem 5:716, [2004]); in that case, the generation of the photocurrent involving an irreversible thiol oxidation at the H₂Pc/water interface took place to be coupled with hole conduction through the H₂Pc layer, based on the photophysical character of the bilayer. In the present work, the photoelectrode characteristics of the bilayer were investigated in the water phase containing a redox molecule , where the photo-induced oxidation and reduction for the couple were found to take place at the bilayer. The photoanodic current involving the oxidation efficiently occurred at the interface of H₂Pc/water, similar to the previous example. In the view of the voltammograms obtained, it was noted that there are pin-holes in the H₂Pc layer of the bilayer, leading to a cathodic reaction with at the PTCBI surface especially in the dark; that is, the band bending at the PTCBI/water interface can essentially be reduced by applying a negative potential [e.g., < ∼ 0 V (vs Ag/AgCl)] to the PTCBI, when the cathodic reaction may take place through the conduction band of the PTCBI. Moreover, under that applied potential condition of irradiation, the photogenerated electron carrier part can move to the PTCBI surface, thus enhancing the reduction of .     

Thermodynamic studies on Pr2TeO6

The standard Gibbs energy of formation of Pr₂TeO₆ $ (\Updelta_{\text{f}} G^{^\circ } \left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} ,\;{\text{s}}} \right)) $ was derived from its vapour pressure in the temperature range of 1,400–1,480 K. The vapour pressure of TeO₂ (g) was measured by employing a thermogravimetry-based transpiration method. The temperature dependence of the vapour pressure of TeO₂ over the mixture Pr₂TeO₆ (s) + Pr₂O₃ (s) generated by the incongruent vapourization reaction, Pr₂TeO₆ (s) = Pr₂O₃ (s) + TeO₂ (g) + ½ O₂ (g) could be represented as: $ { \log }\left\{ {{{p\left( {{\text{TeO}}_{ 2} ,\;{\text{g}}} \right)} \mathord{\left/ {\vphantom {{p\left( {{\text{TeO}}_{ 2} ,\;{\text{g}}} \right)} {{\text{Pa}} \pm 0.0 4}}} \right. \kern-0em} {{\text{Pa}} \pm 0.0 4}}} \right\} = 19. 12- 27132\; \left({\rm{{{\text{K}}}}/T} \right) $ . The $ \Updelta_{\text{f}} G^{^\circ } \;\left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} } \right) $ could be represented by the relation $ \left\{ {{{\Updelta_{\text{f}} G^{^\circ } \left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} ,\;{\text{s}}} \right)} \mathord{\left/ {\vphantom {{\Updelta_{\text{f}} G^{^\circ } \left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} ,\;{\text{s}}} \right)} {\left( {{\text{kJ}}\,{\text{mol}}^{ - 1} } \right)}}} \right. \kern-0em} {\left( {{\text{kJ}}\,{\text{mol}}^{ - 1} } \right)}} \pm 5.0} \right\} = - 2 4 1 5. 1+ 0. 5 7 9 3\;\left(T/{\text{K}}\right) .$ Enthalpy increments of Pr₂TeO₆ were measured by drop calorimetry in the temperature range of 573–1,273 K and heat capacity, entropy and Gibbs energy functions were derived. The $ \Updelta_{\text{f}} H_{{298\;{\text{K}}}}^{^\circ } \;\left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} } \right) $ was found to be $ {{ - 2, 40 7. 8 \pm 2.0} \mathord{\left/ {\vphantom {{ - 2, 40 7. 8 \pm 2.0} {\left( {{\text{kJ}}\,{\text{mol}}^{ - 1} } \right)}}} \right. \kern-0em} {\left( {{\text{kJ}}\,{\text{mol}}^{ - 1} } \right)}} $ .     

Thermochemical properties of di(N,N-di(2,4,6-trinitrophenyl)amino)-ethylenediamine in dimethyl sulfoxide and N-methyl pyrrolidone

The enthalpies of dissolution for di(N,N-di(2,4,6,-trinitrophenyl)amino)-ethylenediamine (DTAED) in dimethyl sulfoxide (DMSO) and N-methyl pyrrolidone (NMP) were measured using a RD496-2000 Calvet microcalorimeter at 298.15?K. Empirical formulae for the calculation of the enthalpies of dissolution (??_diss H) were obtained from the experimental data of the dissolution processes of DTAED in DMSO and NMP. The linear relationships between the rate (k) and the amount of substance (a) were found. The corresponding kinetic equations describing the two dissolution processes were $ {{{\rm{d}}\alpha } \mathord{\left/ {\vphantom {{{\rm{d}}\alpha } {{\rm{d}}t}}} \right. \kern-0em} {{\rm{d}}t}} = 10^{ - 2.68} \left( {1 - \alpha } \right)^{0.84} $ for the dissolution of DTAED in DMSO, and $ {{{\rm{d}}\alpha } \mathord{\left/ {\vphantom {{{\rm{d}}\alpha } {{\rm{d}}t}}} \right. \kern-0em} {{\rm{d}}t}} = 10^{ - 2.79} \left( {1 - \alpha } \right)^{0.87} $ for the dissolution of DTAED in NMP, respectively.     

Gas permeability and permselectivity of fluorinated polybenzoxazoles

Gas permeability and permselectivity are investigated for polybenzoxazoles from bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (BAHHP) and aromatic diacid chlorides. Effects of thermal cyclization on the permeation properties are also investigated. The polybenzoxazole from BAHHP and 4,4′-(1,1,1,3,3,3-hexafluoroisopropylidene)dibenzoyl chloride (HFDB) displays high performance for CO₂/CH₄ separation ( $ {\rm P}_{{\rm CO}_2 } $ = 6.1 × 10^?9 cm³ (STP) cm^?1 s^?1 cm-Hg^?1, and $ {{{\rm P}_{{\rm CO}_2 } } \mathord{\left/ {\vphantom {{{\rm P}_{{\rm CO}_2 } } {{\rm P}_{{\rm CH}_4 } }}} \right. \kern-\nulldelimiterspace} {{\rm P}_{{\rm CH}_4 } }} $ = 38 at 35°C). The polybenzoxazole from BAHHP and 2,6-naphthalene dicarbonyl chloride displays high performance for H₂/CO or H₂/CH₄ separation ( $ {\rm P}_{{\rm H}_2 } $ = 2.4 × 10^?9 cm³ (STP) cm^?1 s^?1 cm-Hg^?1, $ {{{\rm P}_{{\rm H}_2 } } \mathord{\left/ {\vphantom {{{\rm P}_{{\rm H}_2 } } {{\rm P}_{{\rm CO}} }}} \right. \kern-\nulldelimiterspace} {{\rm P}_{{\rm CO}} }} $ = 71, and $ {{{\rm P}_{{\rm H}_2 } } \mathord{\left/ {\vphantom {{{\rm P}_{{\rm H}_2 } } {{\rm P}_{{\rm CH}_{\rm 4} } }}} \right. \kern-\nulldelimiterspace} {{\rm P}_{{\rm CH}_{\rm 4} } }} $ = 250). Permeation properties for the polybenzoxazole from BAHHP and HFDB are close to those for a polyimide of similar chemical structure. The permeation properties are discussed in connection with packing density and local segmental mobility. © 1992 John Wiley & Sons, Inc.     

Kinetics and mechanism of oxidation of the chromium(III)-DL-aspartic acid complex/periodate reaction. Evidence for iron(II) catalysis

The kinetics of oxidation of the chromium(III)-DL- aspartic acid complex, [CrIIIHL]+ by periodate have been investigated in aqueous medium. In the presence of Fe^II as a catalyst, the following rate law is obeyed:

Elektrometrische Untersuchungen über die Geschwindigkeit der Bildung von Cu2S in ammoniakalischen Lösungen von Cu+-Ionen mittels Thioacetamid, 4. Mitt.

Quantitative studies of the rate of Cu₂S-formation by thioacetamide (TAA) were made with the help of the polarographic method of continuous registration at constant potential, and the following equation for the reaction rate between Cu⁺-ions andTAA in ammoniacal solutions was derived: 1 $$ - \frac{{d[Cu^I ]}}{{dt}} = k \cdot \frac{{[Cu^I ] \cdot [CH_3 CSNH_2 ]}}{{[NH_3 H_2 O]^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 2}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{$2$}}} \cdot [H^ + ]}}\frac{{^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 4}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{$4$}}} }}{{^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 {10}}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{${10}$}}} }} \cdot \frac{{f_{Cu} }}{{f_{H^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 {10}}}\right.\kern-\nulldelimiterspace}\!\lower0.7ex\hbox{${10}$}}} } }}$$ The value at 25.0° of the rate constantk is (1.6±0.2)·10^?2 mole^7/20·litre^?7/20·sec^?1. The validity of equation (1) has been proved over the pH range 8.5–9.5 and the ammonia concentration of 4.0·10^?2–4.0·10^?1 mole per litre, by only a small excess ofTAA and moderate reaction rates.     

Etude par Spectrophotometrie d'absorption de l'Equilibre Pu4++Cl−⇋Pu3++1/2 Cl2 dans le melange LiCl−KCl (70–30% mol) fondu

The quantitative study of the equilibrium Pu⁴⁺+Cl⁻⇋Pu³⁺+1/2 Cl₂ in LiCl−KCl (70–30% mol) at 455, 500, 550 and 600°C by visible and near I.R. absorption spectrophotometry allows the calculation of the reaction's equilibrium constant, the mean thermodynamic data ΔH=27±14 kJ·mol⁻¹ and ΔS=37±17 J·mol⁻¹·K⁻¹ and the standard potential of the couple .      

An entanglement model for the dependence of fracture surface energy on molecular weight

Over the last decade, empirical evidence has indicated that the effective surface energy γ associated with the fracture of noncrystalline is a linear function of the reciprocal of the viscosity–average molecular weight: \documentclass{article}\pagestyle{empty}\begin{document}$ \gamma = \gamma _\infty - b\bar M_v ^{ - 1} $\end{document}. For poly(methyl methacrylate), data of J. P. Berry, G. C. Berry and Fox show that gamma; ～ 0 at about the same value of M?_v that corresponds to the polymer chain-entanglement length. From this fact, we have developed an entanglement network model for fracture, that bears a resemblance to F. Bueche's entanglement model for the melt viscosity of bulk polymers. Our model allows for the expression of the previously empirical constants, γ_∞ and b, in terms of molecular parameters: \documentclass{article}\pagestyle{empty}\begin{document}$ {{\gamma _\infty = \gamma _{\rm s} A_{\rm s} Z_{\rm c} \rho _{\rm c} N_A } \mathord{\left/ {\vphantom {{\gamma _\infty = \gamma _{\rm s} A_{\rm s} Z_{\rm c} \rho _{\rm c} N_A } {\bar M_{\rm s} }}} \right. \kern-\nulldelimiterspace} {\bar M_{\rm s} }} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ b = 2({{\bar M_v } \mathord{\left/ {\vphantom {{\bar M_v } {\bar M_n }}} \right. \kern-\nulldelimiterspace} {\bar M_n }})\gamma _\infty M_{\rm f} $\end{document} where M?_n and M?_f are the number-average molecular weights of the polymer and of the free chain ends, M?_v is the viscosity-average molecular weight, γ_s is the average fracture-energy per entanglement in the craze volume, A_s is the average cross-sectional area of the polymer chain, Z_c and ρ_c are the thickness and density of crazed material on the fracture surface, respectively; M?_s is the average strand molecular weight between entanglements, and N_A is AvogadrO's number.     

Effect of the excluded volume on specific rate of combination reactions between polymer radicals

The specific rate k_D for reaction between polymer radicals is formulated when the potential of average force on the basis of the excluded volume affects the motion of the polymer radicals. This rate is given by \documentclass{article}\pagestyle{empty}\begin{document}$ k_D = Fk_S \left( {{\rm with}\ {F} = \sum\limits_{s = 0}^\infty {{{[ ‐ 2(\alpha ^2 ‐ 1)]} \mathord{\left/ {\vphantom {{[ ‐ 2(\alpha ^2 ‐ 1)]} {(s + 1)^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern‐\nulldelimiterspace} 2}} }}} \right. \kern‐\nulldelimiterspace} {(s + 1)^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern‐\nulldelimiterspace} 2}} }}} } \right) $\end{document} where k_S is specific rate of reaction between radical chain ends and α is the average expansion of the polymer arising from the long-range effects. The effect of the excluded volume reduces k_D. F depends on the degree of polymerization of the polymer radical when α ≠ 1. These results are discussed in terms of the experimental data for very low polymer concentrations.     

Relaxation spectra of polymer melts from relaxation and steady-state flow data

Accurate measurements of stress relaxation after steady-state flow have been carried out, in the Newtonian flow region, for a polystyrene and a poly(methyl methacrylate) melt, with a cone-and-plate rotational rheometer. From the stress relaxation σ(t) versus t curves the relaxation spectra H were calculated by means of the first approximation equation: \documentclass{article}\pagestyle{empty}\begin{document}$ H = - ({1 \mathord{\left/ {\vphantom {1 {\dot \gamma t)d\sigma {{(t)} \mathord{\left/ {\vphantom {{(t)} d}} \right. \kern-\nulldelimiterspace} d}}}} \right. \kern-\nulldelimiterspace} {\dot \gamma t)d\sigma {{(t)} \mathord{\left/ {\vphantom {{(t)} d}} \right. \kern-\nulldelimiterspace} d}}}\ln t $\end{document}. The shear stress–shear rate curves, σ versus \documentclass{article}\pagestyle{empty}\begin{document}$ {\dot \gamma } $\end{document} were also measured, in large ranges of shear rates, for the same melts, and from these data the relaxation spectra H were obtained by means of equations given by Faucher and Ferry. The Faucher equation, \documentclass{article}\pagestyle{empty}\begin{document}$ H = - \dot \gamma ^2 d{\sigma \mathord{\left/ {\vphantom {\sigma d}} \right. \kern-\nulldelimiterspace} d}\dot \gamma ^2 $\end{document}, has been found to give results which compare satisfactorily with those obtained from the first approximation equation. It has been found that the Ferry equation has to be modified for comparable agreement.     

Electrodeposition of metals on anodized thin Nb films

The influence of the electronic properties of oxidized Nb surfaces on the electrodeposition of metals (Me=Co, Cu, Ag) with different equilibrium potentials is studied by conventional electrochemical techniques and atomic force microscopy. The results show that relatively thin anodic Nb₂O₅ films (thickness <11 nm) present a frequency-dependent n-type semiconductor behavior, which can be described by the theory of amorphous semiconductor. The Schottky barrier, formed at the a-Nb₂O₅/electrolyte interface, affects the deposition rate of metals with equilibrium potentials more positive than the flat band potential Then, the dependence of density of states on the oxide thickness and anodization conditions leads to different extents of the band bending, affecting directly the rate of electron transfer.     

Phase transitions and thermodynamic properties of anhydrous caffeine

Caffeine has been found to display a low-temperatureβ- and a high-temperatureα-modification. By quantitative DTA the following data were determined: transformation temperature 141±2°; enthalpy of transition 4.03±0.1 kJ·mole^?1; enthalpy of fusion 21.6±0.5 kJ·mole^?1; molar heat capacity $$\begin{array}{*{20}c} {{\vartheta \mathord{\left/ {\vphantom {\vartheta {^\circ C}}} \right. \kern-\nulldelimiterspace} {^\circ C}}} & {100(\beta )} & {100(\alpha )} & {150(\alpha )} & {100(\alpha )} \\ {{{C^\circ _\mathfrak{p} } \mathord{\left/ {\vphantom {{C^\circ _\mathfrak{p} } {J \cdot K^{ - 1} \cdot mole^{ - 1} }}} \right. \kern-\nulldelimiterspace} {J \cdot K^{ - 1} \cdot mole^{ - 1} }}} & {271 \pm 9} & {287 \pm 10} & {309 \pm 11} & {338 \pm 10} \\ \end{array} $$ in good accord with drop-calorimetric data. For the constants of the equation log (p/Pa)=?A/T+B, static vapour pressure measurements on liquid and solidα-caffeine, and effusion measurements on solidβ-caffeine yielded: $$\begin{array}{*{20}c} {A = 3918 \pm 37; 5223 \pm 28; 5781 \pm 35K^{ - 1} } \\ {B = 11.143 \pm 0.072; 13.697 \pm 0.057; 15.031 \pm 0.113} \\ \end{array} $$ . The evaporation coefficient ofβ-caffeine is 0.17±0.03.     

Kinetics and mechanism of the oxidation of hydrogen peroxide by the octacyanotungstate(V) ion in alkaline aqueous media

Summary The oxidation of H₂O₂ by [W(CN)₈]^3– has been studied in aqueous media between pH 7.87 and 12.10 using both conventional and stopped-flow spectrophotometry. The reaction proceeds without generation of free radicals. The experimental overall rate law, , strongly suggests two types of mechanisms. The first pathway, characterized by the pH-dependent rate constant k _s, given by , involves the formation of [W(CN)₈· H₂O₂]^3–, [W(CN)₈· H₂O₂·W(CN)₈]^6– and [W(CN)₈· HO]^3– intermediates in rapid pre-equilibria steps, and is followed by a one-electron transfer step involving [W(CN)₈·HO]^3– (k _a) and its conjugate base [W(CN)₈·O]^4– (k _b). At 25 °C, I = 0.20 m (NaCl), the rate constant with H _a =40±6kJmol^–1 and S _a =–151±22JK^–1mol^–1; the rate constant with H _b =36±1kJmol^–1 and S _b =–136±2JK^–1mol^–1 at 25 °C, I = 0.20 m (NaCl); the acid dissociation constant of [W(CN)₈·HO]^3–, K ₅ =(5.9±1.7)×10^–10 m, with and is the first acid dissociation constant of H₂O₂. The second pathway, with rate constant, k _f, involves the formation of [W(CN)₈· HO₂]^4– and is followed by a formal two-electron redox process with [W(CN)₈]^3–. The pH-dependent rate constant, k _f, is given by . The rate constant k ₇ =23±6m ^–1 s ^–1 with and at 25°C, I = 0.20 m (NaCl).     

The graphical representation of equilibrium for the isothermal and isobaric reactions of ideal gases

The equilibrium for the isothermal and isobaric reactions of ideal gases is investigated in virtue of the intuitionistic figure. The curve is similar to the curve of tangential function which has one inflection and two vertical asymptotes. The equation only has one root ξ _e and it is suitable to find ξ _e by dichotomy. For non-inert substance, when or x_i^0 $$" align="middle" border="0"> , to increase substance i will make an equilibrium shift in the direction to deplete substance i; when {\nu_i} \mathord{\left/ {\vphantom {{\nu_i} {\sum_i {\nu _i}}}} \right. \kern-\nulldelimiterspace} {\sum _i {\nu _i}}> 0$$" align="middle" border="0"> , to increase substance i will make an equilibrium shift in the direction to produce more substance i.     

Polymerization by oxidation coupling. I. A study of the oxidation of 2,6-diphenylphenol to poly(2,6-diphenyl-1,4-phenylene ether)

The synthesis of poly(2,6-diphenyl-1,4-phenylene ether), by the oxidative coupling of 2,6-diphenylphenol has been studied. Procedures were found which demonstrated that polymers of very high molecular weight \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {\overline M _n > 200{\rm 000; }\left[ \eta \right]_{{\rm CHCl}_{\rm 3} }^{25^\circ {\rm C}} > 1.1{\rm }{{{\rm dl}} \mathord{\left/ {\vphantom {{{\rm dl}} g}} \right. \kern-\nulldelimiterspace} g}} \right) $\end{document} could be made with a copper-amine catalyst system. A low nitrogen-to-copper ratio (1 N atom/Cu atom) was necessary to obtain the very high molecular weights under the conditions of these reactions. A variety of amines formed active catalysts; the effectiveness of mono- and bis- primary, secondary, and tertiary amines were compared. Effects of the type of copper halide, reaction temperature, desiccants, addition rates of 2,6-di-phenylphenol, and solvents were also examined. Samples of polymer were isolated at different times during the polymerization. Measurements of viscosity, osmotic pressure, light scattering, gel permeation, phenolic hydroxyl groups, and nitrogen content were made on various samples over a range of intrinsic viscosities of 0.05–0.59 dl/g. A very narrow molecular weight distribution was found for all samples. Hydroxyl endgroup analyses indicated that the concentration of phenolic endgroups per mole of polymer does not change during the polymerization. The presence of some side reactions is indicated by nitrogen analyses. The relationships between the intrinsic viscosity in chloroform at 25°C and M?_n and M?_w are: log [η] = ?3.97 + 0.72₇ log M?_n and log [n] = ?3.56 + 0.62₄ log M?_w.