Determination of equilibrium silver sulphate concentration in the system Cu-H2SO4-CuSO4-H2O-Ag2SO4-Ag as a function of composition

The value of the ratio \(\gamma _{{\text{Cu}}^{{\text{2 + }}} } /\gamma _{{\text{Ag}}^{\text{ + }} }^2 \) ( \(\gamma _{{\text{Cu}}^{{\text{2 + }}} } ,\gamma _{{\text{Ag}}^{\text{ + }} } \) -are the mean activity coefficients of copper and silver ions, respectively) was calculated from the measured emf of the cell $${\text{Cu(Hg)|H}}_{\text{2}} {\text{SO}}_{\text{4}} {\text{ (}}c_{\text{x}} {\text{)}} - {\text{CuSO}}_{\text{4}} {\text{ (}}c_{\text{y}} {\text{)|Hg}}_{\text{2}} {\text{SO}}_{\text{4}} {\text{, Hg}}$$ and the solubility of Ag₂SO₄ in H₂SO₄ (c _x) and CuSO₄ (c _y) solutions. The concentration of H₂SO₄ in the solution was varied from 0.5 to 2.1 mol dm^?3 that of CuSO₄ from 0.4 mol dm^?3 to saturation. The results were presented as a function: $$\frac{{\gamma _{{\text{Cu}}^{{\text{2 + }}} } }}{{\gamma _{{\text{Ag}}^{\text{ + }} }^2 }} = a_0 + a_1 c_{\text{x}} + a_2 c_{\text{y}} + a_3 c_{\text{x}}^{\text{2}} + a_4 c_{\text{x}} c_{\text{y}} + a_5 c_{\text{y}}^2 .$$ This function allows the estimation of the equilibrium silver ion concentration \(c_{{\text{Ag}}^{\text{ + }} }^{{\text{eq}}} \) in solutions containing both H₂SO₄ and CuSO₄ in the presence of metallic copper. The function is also very useful for the estimation of the \(c_{{\text{Ag}}^{\text{ + }} }^{{\text{eq}}} \) near a working copper electrode.     

Polymerization of cyclohexene oxide by methyl-4-[bis(4-bromophenyl)amino]benzoate cation radical salts

Methyl-4-[bis(4-bromophenyl)amino]benzoate cation radical salts having non-nucleophilic anions such as $ {\text{SbF}}^{ - }_{6} $ , $ {\text{PF}}^{ - }_{6} $ and $ {\text{AsF}}^{ - }_{6} $ were newly prepared and found to be very active initiators for the polymerization of cyclohexene oxide at room temperature, in dichloromethane without any external stimulation. The effects of counter ion structure, salt and monomer concentration on the polymerization yield and molecular weight, and the mechanism of initiation are presented.     

Active Sites of a NiSO4/γ-Al2O3 Catalyst for the Oligomerization of Isobutene

Structural characterization, the mechanism of catalytic activity generation and the nature of active sites of a NiSO₄/γ-Al₂O₃ catalyst for isobutene oligomerization were studied by temperature programmed reduction (TPR), X-ray diffraction (XRD), diffuse reflectance infrared fourier transformed (DRIFTS) and X-ray photoelectron spectroscopy (XPS) techniques. The TPR measurements together with the XRD data indicated that calcination of the catalyst at 500 °C did not form either nickel oxide or nickel aluminate. The presence of only one type of surface nickel species formed by the incorporation of nickel ions into the surface vacant sites of γ-alumina lattice was indicated by XPS with Ar⁺ ions sputtering and TPR measurements. XPS analysis of the calcined catalyst suggested that the oxidation state of nickel ions in the calcined catalyst was (+2) and after calcination the nickel ions were coordinated to relatively more basic ligands. The surface acid centers of the catalyst were found to be only Lewis type. SO₄ ^2? ions were found to be present as a chelating bidentate ligand and enhanced the acidity of metal ( $ {\text{Al}}^{3 + } $ and/or $ {\text{Ni}}^{2 + } $ ) Lewis acid centers. The results suggested that the combined effects of the presence of the bidentate SO₄ ^2? ligand and dehydroxylation generate coordinatively unsaturated $ {\text{Ni}}^{2 + } $ that interact with isobutene during the oligomerization reaction. The formation of lower-valent nickel ions ( $ {\text{Ni}}^{x + } ,x\; \le\; 1 $ ) was demonstrated by in situ DRIFTS using CO as a probe molecule and by XPS measurements. Formation of a binuclear bridging carbonyl complex, $ [{\text{Ni}}({\text{CO}})^{ + } ]_{2} $ suggested that some lower-valent nickel species were formed via in situ reduction by isobutene. Analysis of Ni 2p photolines indicated the appearance of a new lower-valent nickel species ( $ {\text{Ni}}^{x + } ,x \;\le\; 1 $ ) during the course of isobutene oligomerization. Hence it is plausible that lower-valent nickel species might act as the active center for the oligomerization reaction, while the SO₄ ^2? ions enhance the acidity of the Lewis acid sites on the surface and assist in the adsorption of reactant molecules on the surface.     

Facile Electrospinning Preparation and Up-Conversion Luminescence Performance of Y3Al5O12:Er3+, Yb3+ Nanobelts

Electrospinning technique was used to prepare $ {\text{PVP}}/\left[ {{\text{Y}}\left( {{\text{NO}}_{ 3} } \right)_{ 3} + {\text{Yb}}\left( {{\text{NO}}_{ 3} } \right)_{ 3} + {\text{Er}}\left( {{\text{NO}}_{ 3} } \right)_{ 3} + {\text{Al}}\left( {{\text{NO}}_{ 3} } \right)_{ 3} } \right] $ composite nanobelts and novel structures of Y₃Al₅O₁₂:Er³⁺, Yb³⁺ (denoted as YAG:Er³⁺, Yb³⁺ for short) nanobelts have been successfully fabricated after calcination of the relevant composite nanobelts at 900 °C for 8 h. YAG:Er³⁺, Yb³⁺ nanobelts were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and fluorescence spectroscopy. XRD analysis indicated that YAG:Er³⁺, Yb³⁺ nanobelts were cubic in structure with space group I_a3d. SEM analysis and histograms revealed that the width of YAG:Er³⁺, Yb³⁺ nanobelts was ca. 1.8 ± 0.37 μm under the 95 % confidence level, and the thickness was ca. 81.8 nm. Up-conversion emission spectra analysis manifested that YAG:Er³⁺, Yb³⁺ nanobelts respectively emitted strong green and red emissions centering at 522, 554 and 648 nm under the excitation of a 980-nm diode laser. The green emissions were assigned to the energy levels transitions of $ ^{ 2} {\text{H}}_{ 1 1/ 2} ,^{ 4} {\text{S}}_{ 3/ 2} \to^{ 4} {\text{I}}_{ 1 5/ 2} $ of Er³⁺ ions, and the red emission originated from the energy levels transition of $ ^{ 4} {\text{F}}_{ 9/ 2} \to ^{ 4} {\text{I}}_{{{\text{l5}}/ 2}} $ of Er³⁺ ions. The up-conversion luminescence of YAG:Er³⁺, Yb³⁺ nanobelts doped with various concentrations of Yb³⁺ and Er³⁺ was studied and the optimum molar ratio of Yb³⁺ to Er³⁺ was found to be 15:1. CIE analysis demonstrated that color-tuned luminescence can be obtained by adjusting doping concentrations of Yb³⁺ and Er³⁺ ions, which could be applied in the fields of optical telecommunication and optoelectronic devices. The up-conversion luminescent mechanism and the formation mechanism of YAG:Er³⁺, Yb³⁺ nanobelts were also proposed.     

The Effect of CO2 and H2O on the Kinetics of NO Reduction by CH4 Over Sr-Promoted La2O3

The influence of CO₂ and H₂O on the activity of 4% Sr-La₂O₃ mimics that observed with pure La₂O₃, and a reversible inhibition of the rate is observed. CO₂ causes a greater effect, with decreases in rate of about 65% with O₂ present and 90% in its absence, while with H₂O in the feed, the rate decreased around 35-40% with O₂ present or absent. The influence of these two reaction products on kinetic behavior can be described by assuming competitive adsorption on the surface, incorporating adsorbed CO₂ and H₂O in the site balance, and using rate expressions previously proposed for this reaction over Sr-promoted La₂O₃. In the absence of O₂, the rate expression is $$r_{N_2 } = \frac{{k'P_{{\text{NO}}} P_{{\text{CH}}_{\text{4}} } }}{{{\text{(1 + }}K_{{\text{NO}}} P_{{\text{NO}}} {\text{ + }}K_{{\text{CH}}_{\text{4}} } P_{{\text{CH}}_{\text{4}} } {\text{ + }}K_{{\text{CO}}_{\text{2}} } P_{{\text{CO}}_{\text{2}} } {\text{ + }}K_{{\text{H}}_{\text{2}} {\text{O}}} P_{{\text{H}}_{\text{2}} {\text{O}}} {\text{)}}^{\text{2}} }},$$ which yields a good fit to the experimental data and gives optimized equilibrium adsorption constants that demonstrate thermodynamic consistency. With O₂ in the feed, nondifferential changes in reactant concentrations through the reactor bed were accounted for by assuming integral reactor behavior and simultaneously considering both CH₄ combustion and CH₄ reduction of NO, which provided the following rate law for total CH₄ disappearance: $$(r_{{\text{CH}}_{\text{4}} } )_{\text{T}} = \frac{{k'_{{\text{com}}} P_{{\text{CH}}_{\text{4}} } P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} + k'_{{\text{NO}}} P_{{\text{NO}}} P_{{\text{CH}}_{\text{4}} } P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} }}{{{\text{(1 + }}K_{{\text{NO}}} P_{{\text{NO}}} {\text{ + }}K_{{\text{CH}}_{\text{4}} } P_{{\text{CH}}_{\text{4}} } {\text{ + }}K_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} {\text{ + }}K_{{\text{CO}}_{\text{2}} } P_{{\text{CO}}_{\text{2}} } {\text{ + }}K_{{\text{H}}_{\text{2}} {\text{O}}} P_{{\text{H}}_{\text{2}} {\text{O}}} {\text{)}}^{\text{2}} }}.$$ The second term of this expression represents N₂ formation, and it again fit the experimental data well. The fitting constants in the denominator, which correspond to equilibrium adsorption constants, were not only thermodynamically consistent but also provided entropies and enthalpies of adsorption that were similar to values obtained with other La₂O₃-based catalysts. Apparent activation energies typically ranged from 23 to 28 kcal/mol with O₂ absent and 31-36 kcal/mol with O₂ in the feed. With CO₂ in the feed, but no O₂, the activation energy for the formation of a methyl group via interaction of CH₄ with adsorbed NO was determined to be 35 kcal/mol.     

Conduction in Bi2O3-based oxide ion conductor under low oxygen pressure. II. Determination of the partial electronic conductivity

In order to investigate the partial electronic conduction in the high oxide ion conductor of the system Bi₂O₃-Y₂O₃ under low oxygen pressure, e.m.f. and polarization methods were employed. Although the electrolyte was decomposed when the \(P_{{\text{O}}_{\text{2}} }\) was lower than the equilibrium \(P_{{\text{O}}_{\text{2}} }\) of Bi, Bi₂O₃ mixture at each temperature, the ionic transport number was found to be close to unity above that \(P_{{\text{O}}_{\text{2}} }\) . The hole conductivity (σ _p) and the electron conductivity (σ _p) could be expressed as follows, $$\begin{gathered} \sigma _p \Omega cm = 5 \cdot 0 \times 10^2 \left( {P_{O_2 } atm^{ - 1} } \right)^{{1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} \exp \left[ { - 106 kJ\left( {RT mol} \right)^{ - 1} } \right] \hfill \\ \sigma _p \Omega cm = 3 \cdot 4 \times 10^5 \left( {P_{O_2 } atm^{ - 1} } \right)^{ - {1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} \exp \left[ { - 213 kJ\left( {RT mol} \right)^{ - 1} } \right] \hfill \\ \end{gathered} $$ These values were much lower than the oxide ion conductivity under ordinary oxygen pressure.     

Controlling Reaction Pathways for Alcohol Dehydration and Dehydrogenation over FeSBA-15 Catalysts

The iron location in FeSBA-15 strongly influences the selectivity to dehydrogenation and dehydration in ethanol conversion. At low iron loading, Fe is present as isolated $\hbox{Fe}^{3+}The iron location in FeSBA-15 strongly influences the selectivity to dehydrogenation and dehydration in ethanol conversion. At low iron loading, Fe is present as isolated species in the amorphous silica phase. At higher loading additional aggregated forms of iron oxide exist. Isolated species in the silica matrix imply Br?nsted acidity resulting in selective formation of ethylene, whereas clusters catalyze formation of ethylene and aldehyde.     

Effects of Root Exudates of Cucumber (Cucumis sativus) and Allelochemicals on Ion Uptake by Cucumber Seedlings

The effects of root exudates of cucumber, aromatic carboxylic acids in root exudates, and their analogs upon the uptake of NO₃, $H_2 PO_4^ - $ $SO_4^{2 - } $ K⁺, Ca²⁺, Mg²⁺, and Fe²⁺ by intact cucumber seedlings were examined. Root exudates inhibited the uptake of all the ions analyzed except for $H_2 PO_4^ - $ . Inhibition of ion uptake by cinnamic acid, a main component of root exudates, was both concentration- and pH-dependent. With decreasing pH, the inhibitory effect on the ion uptake increased. With benzoic and cinnamic acids, the substitution of hydrophilic group(s) on the benzene ring alleviated the inhibition of ion uptake. Aromatic acids enhanced ion leakage. The potency was in proportion, but not equal, to the extent of uptake inhibition. The lipophilicity was a valuable index for evaluating the allelopathic potential of aromatic acids.     

镍铝层状双金属氢氧化物的亲油改性及其吸油性能

Ni^(2+)与Al^(3+)物质的量比为3∶1,尿素为沉淀剂,通过水热合成技术制备镍铝层状双金属氢氧化物层状材料(Ni^(2+)-Al^(3+)-CO_3^(2-)-LDHs)。以Ni^(2+)-Al^(3+)-CO_3^(2-)-LDHs为前驱体,分别与Na Cl和十二烷基磺酸钠[CH_3(CH_2)_(11)SO_3Na]进行离子交换反应得到Ni^(2+)-Al^(3+)-CH_3(CH_2)_(11)SO_3^--LDHs新型吸附剂材料。将CH_3(CH_2)_(11)SO_3^-亲油客体负载到Ni^(2+)-Al^(3+)-LDHs层状材料层间,实现镍铝层状双金属氢氧化物的亲油改性。利用Ni^(2+)-Al^(3+)-CH_3(CH_2)_(11)SO_3^--LDHs复合材料对含油污水进行处理,结果表明,镍铝层状双金属氢氧化物亲油改性后增强了LDHs的亲油吸附性能。     

Electrochemical study of catalytic oxidation of naphthalene in molten sulphate pyrosulphate at 425° C with vanadium pentoxide

Naphthalene oxidation in a molten mixture of potassium sulphate pyrosulphate at 425° C in the presence of vanadium pentoxide takes place in three stages. The electrochemical study of each stage has led to the proposal of kinetic equations for the initial rates: (i) naphthalene oxidation by the medium $$V_1^0 = 2 x 10^{ - 2} P_{C_{10} H_8 }$$ (ii) mixture regeneration by V₂O₅ $$V_2^0 = 19.2 x 10^{ - 2} P_{SO_2 }$$ (iii) catalyst regeneration by oxygen $$V_3^0 = 82.8P_{O_2 } [V(IV)]^2$$ This shows that the molten salt acts not only as a solvent but also as a reagent in the catalytic process.     

Heteronuclear Cu(II)–Mn(II)–Cu(II) Complex Constructed from Metallo-Ligand Through Carboxylate Oxygens: Coexistence of Water Hexamers

A heteronuclear complex of [Mn(H₂O)₄(CuL)₂]₂·4H₂O 1 (H₂L = 2-hydrogen benzaldehydeneglycylglycine) has been synthesized and characterized by IR spectra, TGA, and single crystal X-ray diffraction analysis. The molecule consists of one $\text{Mn}{(\text{H}_{2}\text{O})_{4}}^{2+}$ Mn(H₂O) ₄ ²⁺ group and two symmetric groups [CuL]^? which are connected by carboxylate oxygen atoms. A discrete water hexamer composed of a planar tetrameric water ring and two pendent water molecules acts as a ‘glue’ to assemble adjacent [CuL]^? into a two-dimensional structure.     

A simple and efficient oxidation system for the oxidation of alcohols utilizing Oxone® as oxidant catalyzed by polymer-supported 2-iodobenzamide

$\begin{array}{l}{\hbox{R}^1\hbox{R}^2\hbox{CHOH}} \\ {\hbox{RCH}_2\hbox{OH} }\end{array} \dynrightarrow{Oxone}{\hbox{CH}_3\hbox{CN/H}_2\hbox{O}, 70^{\circ}\hbox{C}} \begin{array}{l}{\hbox{R}^1\hbox{R}^2\hbox{CO}} \\ {\hbox{RCOOH}} \end{array} A simple and environmentally friendly procedure for the oxidation of alcohols is presented utilizing Oxone^? (2KHSO₅ · KHSO₄ · K₂ SO₄) as oxidant and polymer-supported 2-iodobenzamide as catalyst in CH₃CN/H₂O mixed solvents.     

Mass transfer in annular electrolytic cells with gas stirring

Mass transfer towards the inner electrode and the wall electrode was studied in an annular cell stirred with an inert gas bubble flow. Experimental data obtained for the wall electrode follow the relationship found previously for circular cells; namely $$Sh = 0.231(ScGa)^{1/3} (L/D_e )^{ - 0.194_\varepsilon0.246}$$ Study of the influence of gas hold-up on the mass transfer rate towards the inner wall electrode has yielded the following relationship: $$Sh_\infty= 0.315(ScGa)^{1/3_\varepsilon0.231}$$      

Magnetic cobalt-zinc ferrite/PVAc nanocomposite: synthesis and characterization

Metal oxide nanoparticles are the subject of current interest because of their unusual optical, electronic, and magnetic properties. In this work, cobalt zinc ferrite ( $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ ) nanoparticles have been synthesized successfully through redox chemical reaction in aqueous solution. The synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles have been used for the preparation of homogenous polyvinyl acetate-based nanocomposite ( $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} /{\text{PVAc}} $ ) via in situ emulsion polymerization method. Structural, morphological and magnetic properties of the products were determined and characterized in detail by X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The XRD patterns of the $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ confirmed that the formed nanoparticles are single crystalline. According to TEM micrographs, the synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles had nano-needle morphology with an average particle size of 20 nm. The calculated coefficient of variation (CV) of nanoparticles diameters obtained by TEM micrographs was 16.77. The $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles were dispersed almost uniformly in the polymer matrix as was proved by SEM technique. The magnetic parameters of the samples, such as saturation magnetization (M _s) and coercivity (H _c) were measured, as well. Magnetization measurements indicated that the saturation magnetization of synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} /{\text{PVAc}} $ nanocomposites was markedly less than that of $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ magnetic nanoparticles. However, the nanocompoites exhibited super-paramagnetic behavior at room temperature under an applied magnetic field.     

[CuL(H2O)2]{[CuL][Fe(CN)6]}2·2H2O (L=3,10-Bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane): A Novel Three-Dimensional Coordination Polymer via H-Bonded Linkages of One-Dimensional Zigzag Chain

A complex with the formula [CuL(H₂O)₂]{[CuL][Fe(CN)₆]}₂·2H₂O, where L=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, has been synthesized and crystallographically characterized. The structure is composed of a one-dimensional zigzag chain of $\left\{ {[{\text{CuL}}][{\text{Fe(CN)}}_{\text{6}} ]} \right\}_2^{2 - } $ units, and [CuL(H₂O)₂]²⁺ units. The one-dimensional zigzag chain extents through ${\text{Cu}}{\kern 1pt} - {\kern 1pt} {\text{CN}} - {\kern 1pt} {\text{Fe}}{\kern 1pt} - {\kern 1pt} {\text{CN}} - {\kern 1pt} {\text{Cu}}$ linkages. The adjacent two polymer chains are linked by the ${\text{O}}{\kern 1pt} - {\kern 1pt} {\text{H}}{\kern 1pt} \cdot \cdot \cdot {\kern 1pt} {\text{N}}{\kern 1pt} \equiv {\kern 1pt} {\text{C}}{\kern 1pt} - $ hydrogen bonding between [CuL(H₂O)₂]²⁺ and [Fe(CN)₆]^3?, forming a 3D supramolecular structure with inner hydrophilic channels. Magnetic susceptibility measurements show no exchange interaction between the Cu(II) and Fe(III) ions due to the longer ${\text{Cu}}{\kern 1pt} - {\kern 1pt} {\text{N}}$ (axial) bond length.     

Positive polyacetylene electrodes in aqueous electrolytes

Polyacetylene films, contacted with platinum mesh, have been polarized anodically in aqueous H₂SO₄, HClO₄, HBF₄ and H₂F₂ of medium concentrations (30–70 wt%). Two oxidation peaks are observed, the equivalents of which are 1 $${\text{(1) 0}}{\text{.045 F mol}}^{ - {\text{1}}} {\text{ CH (2) 0}}{\text{.23 F mol}}^{ - {\text{1}}} {\text{ CH}}$$ The potential of the Process 1 decreases linearly with increasing acid concentration by 20–40 mV mol^?1 dm^?3, while the potential of Peak 2 exhibits normal Nernst behaviour (about + 60 mV decade^?1. Process 1 is partially reversible, while Process 2 is totally irreversible. From these findings for Process 1 we conclude the reversible insertion of anions into the polyacetylene host lattice, which is primarily oxidized to the polyradical cation, with the co-insertion of acid molecules HA to yield the insertion compound [(CH)⁺·yA^?·vyHA] _x y?4.5% andv=1.5 for H₂SO₄ and HClO₄. In the course of Process 2, the polymer is irreversibly oxidized according to $$( - ^ \cdot {\text{CH}} \cdot \cdot \cdot \cdot \cdot \cdot \cdot \cdot ^ \oplus {\text{ CH}} - )_{x/2} + 2{\text{H}}_{\text{2}} {\text{O}} \to ( - \mathop {\text{C}}\limits_{\mathop \parallel \limits_{\text{O}} } \cdot \cdot \cdot \cdot \cdot \cdot \cdot \cdot \mathop {\text{C}}\limits_{\mathop \parallel \limits_{\text{O}} } - )_{x/2} + 6{\text{H}}^{\text{ + }} + 5e^ - $$ As this process occurs to some extent even in the potential region of Process 1, a continuous degradation of the host lattice occurs upon cycling.     

Hansen solubility parameters of cellulose acetate butyrate–poly(caprolactone) diol blend by inverse gas chromatography

The specific retention volumes, $ V_{\text{g}}^{0} $ , for adsorption of 21 solute probes on the solid surface of cellulose acetate butyrate (CAB)–poly(caprolactone) diol (PCLD) blend determined in the temperature range by inverse gas chromatography were used to evaluate Hansen solubility parameters (HSP). The effect of plasticizer, PCLD, on the HSP of CAB was investigated. The three components of HSP namely dispersive $ \delta_{2}^{\text{d}} $ , polar $ \delta_{2}^{\text{p}} $ , and hydrogen bonding $ \delta_{2}^{\text{h}} $ of the blend surface were compared with the CAB surface. The $ \delta_{2}^{\text{h}} $ of CAB was increased due to the addition of PCLD, while the change in the dispersive and polar components was found to be insignificant. The three HSP were decreasing linearly with increase of temperature for the blend as well as for pure CAB. The variation of HSP with weight fraction of CAB shown that the $ \delta_{2}^{\text{p}} $ was positively deviating from linearity whereas $ \delta_{2}^{\text{d}} $ and $ \delta_{2}^{\text{h}} $ were negatively deviating from linearity.     

Mass transfer in electrolytic cells with gas stirring

Mass transfer to wall electrodes was investigated in a circular cell agitated by gas bubbles. Perforated and porous plates were used as gas spargers. Electrodes with varying height and electrolytic solutions having different physical properties were tested. It was found that the enhancing effect of gas bubbles on the mass transfer coefficient is a function of the gas hold-up, irrespective of the velocity of the gas flow and the gas distributor employed. The results were correlated for short mass transfer lengths by the relationship $$Sh = 0.231(ScGa)^{\frac{1}{3}} (L/D_c )^{--0.194 _\varepsilon 0.246}$$ and for fully developed mass transfer by $$Sh_\infty = 0.256(ScGa)^{\frac{1}{3}} \varepsilon ^{0.254}$$      

Structure and Spectral Properties of Pyrazine Ligand Assisted Self-Assembly of a Coordination Polymer Containing Copper-Cyanide Building Blocks

The metal–organic framework $ ^{3}_{\infty } \left[ {{\text{Cu}}_{3} \left( {\text{CN}} \right)_{3} \cdot \left( {\text{pyz}} \right)_{ 2} } \right] $ ∞ 3 [ Cu 3 ( CN ) 3 · ( pyz ) 2 ] , 1, (pyz pyrazine) was prepared in water/acetonitrile solvent at ambient temperature from the adducts K₃[Cu(CN)₄], pyrazine and Me₂SnCl₂. The structure of 1 consists of four-coordinate Cu(1) sites exhibiting a distorted tetrahedral geometry and the linear two-coordinate Cu(2) sites. Notably distorted cages, [Cu₈(CN)₄(pyz)₄], [Cu₈(CN)₆(pyz)₂] and [Cu₆(CN)₂(pyz)₄], can be considered as the basic building blocks of the structure of 1. Box-like structures create inextricably interpenetrated equivalent 3D-frameworks. The structure and spectroscopic properties of 1 were also investigated by thermal analysis and IR, mass, UV/Vis and fluorescence spectra.     

Comportement electrochimique de NbCl5 en milieu NaCl-KCl pur et additionne d'ions fluorure

Dans le domaine de température 700–800°C, les solutions d'ions niobium obtenues par addition de NbCl₅ dans le melange équimolaire NaCl-KCl, sont réduites jusqu'au métal en une seule étape: $${\text{Nb(IV) }} + {\text{ 4e}}^ - \Leftrightarrow {\text{Nb(o)}}$$ Cet échange est réversible, il lui correspond le potentiel standard apparent: $$E_{Nb(IV)/Nb}^{'0} = - 0.64V(Ag - AgCl) \pm 0.01V$$ Les espéces Nb(iv) sont oxydées selon le processus réversible: $${\text{Nb(IV)}} \Leftrightarrow {\text{Nb(v)}} + {\text{e}}^ -$$ Le potentiel standard apparent associé est: $$E_{Nb(IV)/Nb}^{'0} = - 0.74V(Ag - AgCl) \pm 0.05V$$ L'ajout d'ions fluorure déstabilise le complexé NbCl₆ ^2? au profit du complexe NbF₆ ^2? . Ceci se traduit par un déplacement du pie cathodique vers des potentiels plus cathodiques mais le mécanisme de réduction comporte toujours une seule étape mettant en jeu quatre électrons. Dans ces milieux des dépôts de niobium métallique ont eté obtenus caractérisés par rayon X. In the 700–800°C temperature range, NbCl₅ solutions in equimolar NaCl-KCl mixtures are reduced to the metal through a single step: $${\text{Nb(IV)}} + 4{\text{e}}^ - \Leftrightarrow {\text{Nb(o)}}$$ This exchange is reversible and the corresponding apparent standard potential is: $$E_{Nb(IV)/Nb}^{'0} = - 0.64V(Ag - AgCl) \pm 0.01V$$ The Nb(iv) species are oxidized according to the following reversible process: $${\text{Nb(IV)}} \Leftrightarrow {\text{Nb(v)}} + {\text{e}}^ -$$ The associated apparent standard potential is: $$E_{Nb(IV)/Nb}^{'0} = - 0.74V(Ag - AgCl) \pm 0.05V$$ The addition of fluoride ions destabilizes the NbCl₆ ^2? complex and yields the NbF₆ ^2? complex. The cathodic peak potential moves toward more cathodic potentials, but the reduction mechanism still involves a single step with four electrons exchanged. In these media, metallic niobium deposits have been obtained, and characterized through X-ray analysis.