Characterization of polyvinyl chloride part II. The unperturbed end to end distance values obtained from a new GPC method and viscometry

A new gel permeation chromatography (GPC) method is proposed for determining the unperturbed end-to-end distance, \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} $\end{document}, of polymers of known molecular weights, Mn and Mw. This method requires the value of \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} _{{\rm ps}} $\end{document} of polystyrene which was determined through viscometry to be 0.735 \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{{\rm {\AA}}^2-{\rm mole}}}{{gm}}} \right)^{0.5} $\end{document} Polyvinyl chloride (PVC) was chosen to illustrate the method and \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2}}{M}} \right)^{0.5} _{pvc} $\end{document} was found to be 0.99 from GPC data which is in agreement with the result obtained from viscometry, \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2}}{M}} \right)^{0.5} _{pvc} $\end{document} = 1.01. All \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} $\end{document} values were determined at 30°C. The advantage to this method lies in its speed and economy of materials.     

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.     

Analysis of the kinetics for the H2 + - \frac{1}{2}O2 ⇌ H2O reaction on a hot Pt surface in the pressure range 0.10–10 Torr

The H₂ + O₂ ⇌ H₂O reaction on platinum at 700 and 1300 K has been studied. A stagnation flow geometry was used with a gas mixture of H₂ and O₂ at pressures between 0.10 and 10 Torr. Comparing SHG results with simulations using different reaction parameters, it was concluded that , and . LIF measurements showed an ambiguity in the choice of main water-producing channel. Both hydrogen addition with low sticking coefficients and hydroxyl disproportionation with high sticking coefficients are plausible. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

A study of the fatigue behavior of fiber reinforced nylons

A phenomenological model combining a Weibull distribution function with a kinetic equation for flaw growth has been used to describe the static tensile strengths and fatigue lives of short graphite-fiber reinforced nylon 66 materials. A simple Weibull function of the form \documentclass{article}\pagestyle{empty}\begin{document}$ P\left( {\sigma _b } \right) = \exp - \left( {{{\sigma _b } \mathord{\left/ {\vphantom {{\sigma _b } {\hat \sigma }}} \right. \kern-\nulldelimiterspace} {\hat \sigma }}} \right)^{9.5} $\end{document} described the distribution of static strengths. The scale factor \documentclass{article}\pagestyle{empty}\begin{document}$ {\hat \sigma } $\end{document} varies with the annealing treatment and, in general, is a function of environmental variables. The cumulative distribution of breaking times in fatigue can be characterized by a translated three parameter Weibull function \documentclass{article}\pagestyle{empty}\begin{document}$ P\left( {t_B } \right) = \exp - \left\{ {\left. {\left( {\frac{{\sigma _{\max } }}{{\hat \sigma }}} \right)^{16} + \frac{{t_B }}{{\hat t}}} \right\}} \right.^{0.59} . $\end{document} The average time to break (which is related to the time scale factor \documentclass{article}\pagestyle{empty}\begin{document}$ {\hat t} $\end{document}), appears to be a function of the flaw growth rate. The distribution equation has been found to predict the number of half cycle failures and is thus a valid model for the proof testing of large populations. An electrical resistivity method was developed to measure flaw growth rates in prenotched cantilever beams. Experimental data fit the following equation: ln (Δa/Δn) = ?88.88 + (12.46 ± 5.68) ln (K_eff)_max. The correlation coefficient was 0.81. From curve fitting of fatigue data it appeared that flaw growth rate varied with the ninth power of flaw length (Δa/Δn) = Ma⁹. The direct measure of flaw growth rate using electrical resistance gave Δa/Δn = Ma^6.23±2.84 with 90 percent confidence. The two measurements overlap within the 90 percent confidence bands, but predictions of fatigue life using the flaw propagation data were not good. Scanning electron microscope studies showed that specimens with a short fatigue life have glassy, fibrillated fracture surfaces while specimens with a long fatigue life exhibit a high degree of ductility in portions of the fracture surface. These differences are traced to differences in the size and shape of flaws.     

Zur kinetik der acrylnitril-polymerisation

The heterogeneous bulk polymerization of acrylonitrile initiated by AIBN has been studied by means of an improved dilatometric technique and a new method of analysis, where the initial reaction rate (v_w)₀ results from the intercept of a straight line in a \documentclass{article}\pagestyle{empty}\begin{document}$ \frac {\ln \left( 1 \hbox{---} {\rm U} \right)} {{\rm e}^{{- 0,5} {\rm k}_{\rm s}{\rm t} \hbox{---} 1}}$\end{document} versus t plot. It has been found that the initial reaction rate is proportional to the square root of the initial catalyst concentration S₀. The ratio of the rate coefficients of propagation and termination\documentclass{article}\pagestyle{empty}\begin{document}$\frac { {\rm k}_{\rm a} } { {\rm k}_{ {\rm w}^{2} } } $\end{document} could be calculated from the slope of a straight line passing through the origin in a plot of (v_w)₀ versus \documentclass{article}\pagestyle{empty}\begin{document}$\sqrt { {\rm S}_{0} }$\end{document} and yielded a value of 280 mol 1^?1.     

Kinetic study of the hydrolysis of cellulose acetate in the pH range of 2–10

A kinetic study of the hydrolysis of 39.8 wt.-% acetyl cellulose acetate has been made as a function of pH and temperature over the pH range of 2.2–10 and temperature range of 23–95°C. The hydrolysis reaction was carried out on highly porous membranes under quasihomogeneous conditions and the data have been treated as a pseudo-first-order reaction in acetyl concentration. The reaction can be represented by the equation \documentclass{article}\pagestyle{empty}\begin{document}$k_1 {\rm = }\;k_{\rm H ^ +} \left[ {{\rm H^+}} \right]{\rm +}k_{\rm OH^-}\left[ {{\rm OH}^ - } \right] + k_{\rm H_2O} $\end{document}, and where \documentclass{article}\pagestyle{empty}\begin{document}$k_{\rm H} ^ + {\rm = 5}{\rm .24}\;{\rm x 10}^{\rm 5} {\rm exp }\left\{ {{\rm ‐ 16}{\rm .4 x 10}^{\rm 3} /RT} \right\},{\rm }k_{{\rm OH}} ^ ‐ {\rm = 1}{\rm .55}\;{\rm x 10}^{\rm 4} {\rm exp }\left\{ {{\rm ‐ 8}{\rm .1 x 10}^{\rm 3} /RT} \right\}$\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$k_{\rm H_2O} {= 4.25\;\times 10}^{- 2} {\rm exp }\left\{ {{- 11.5 \times 10^3 /RT}} \right\}$\end{document} (where the quantities in brackets are activities of the ions shown).     

Massenspektrometrische Fragmentierung cis/trans-isomerer tert. Butylcycloheptanole

Mass Spectrometric Fragmentation of cis-trans Isomeric tert. Butylcycloheptanols The mass spectra of six cis-trans isomeric tert. butylcycloheptanole 1 – 6 are discussed The fragmentation of the tert. butylcycloheptanols is similar to that observed for the corresponding cyclohexanes. The quotient \documentclass{article}\pagestyle{empty}\begin{document}$ \frac{{[{\rm M \hbox{---} M}_{\rm 2} {\rm O}]^{+ _ \bullet}}}{{{\rm M}^{{\rm +}_ \bullet}}} $\end{document} is found to be characteristic for the different geometric isomers. But the differences observed between flexible tert. butylcycloheptanols are much smaller than those calculated for the rigid tert. butylcyclohexanols.     

Differentiation of Competitive vs. Non-competitive Mechanisms Mediating Disruption of Moth Sexual Communication by Point Sources of Sex Pheromone (Part 2): Case Studies

Eleven out of 13 disruption profiles (plots of dispenser density vs. male catch) from moth sex pheromone literature were consistent with a competitive-attraction mechanism, in which dispensers attract males and thereby divert them from females. Mean dispenser activity (D _a) across all competitive-attraction cases was 0.04 ± 0.06 (SD); values ranged from 0.0005 for a tiny laminated flake dispenser of racemic disparlure targeting gypsy moth to 0.2 for polyethylene tube dispensers used against lightbrown apple moth. A dispenser application activity () can be calculated by multiplying D _a by the number of such dispensers applied per hectare of crop. The highest dispenser application activity () values approached 200 and corresponded to >99% inhibition of catches of male moths in monitoring traps. Relative to the scale, % inhibition of catches of male moths compressed and obscured large differences in when % disruption exceeded 90%. For cases of competitive attraction, these two efficacy scales can be interconverted by using the formula: . When disruptive point sources of pheromone were directly observed, male moths were seen approaching pheromone dispensers whose disruption profiles matched competitive attraction. Two cases fit non-competitive disruption mechanisms, which include camouflage, desensitization (adaptation and/or habituation), and sensory imbalance. In these cases, pheromone was released at rates higher than for cases of disruption by competitive attraction. Practical ramifications of the finding that competitive attraction appears to be the prevalent mechanism for moth mating disruption by pheromone point sources are listed. We believe that the congruence of diverse sets of mating disruption field data with explicit a priori predictions validates competitive-attraction theory. The analytical tools and principles governing competitive attraction that were uncovered during this study of mating disruption of moths should be generally applicable to competitive-attraction phenomena.     

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.     

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 at the electrodes of the ‘falling-film cell’

In the falling-film cell the electrolyte flows as a thin film in the channel between an inclined plane plate and a sheet of expanded metal which work as electrodes. The present work gives the mass transfer coefficients at both electrodes; the experimental variables are the electrolyte flow-rate, the angle of inclination of the channel and the interelectrode distance. The results allow three different flow regimes to be characterized. At low flow rates, there exists a particular regime where capillary effects are present; in this regime the mass transfer coefficient decreases with increasing flow rate, which is interesting from the point of view of possible industrial electrolytic applications.Nomenclature b width of the inclined channel - D diffusion coefficient - d interelectrode distance - e _m mean film thickness - Grashof number, based ond - Grashof number, based onL - ¯k overall mass transfer coefficient, defined by Equation 9 - L electrode length - Q _v volumetric flow rate - volumetric flow rate per unitQ _vl width of channel - Reynolds number - Schmidt number - Sherwood number, based ond - Sherwood number, based onL - mean velocity of the liquid film - inclination angle of the channel with respect to the horizontal - kinematic viscosity of them electrolyte     

The Radiation Chemistry of Cytochrome c

The literature on the reaction of cytochrome c with the radiolytically generated radicals \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm e}_{{\rm eq}}^ -,^. {\rm OH,}^{\rm .} {\rm H,CO}_2^ -,{\rm O}_{\rm 2}^ -,{\rm Br}_{\rm 2}^ - $\end{document} and various organic radicals is reviewed. It would appear that negatively charged radicals, aided by the electric field of cytochrome c, react at the exposed haem edge. Uncharged organic radicals also react at this site. \documentclass{article}\pagestyle{empty}\begin{document}$ ^. {\rm H} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ ^. {\rm OH} $\end{document} are likely to reduce the prosthetic group indirectly by a tunnelling mechanism.     

Study of mass transfer in a vertically moving particle bed electrode

A study was made of the influence of process parameters on the mass-transfer coefficient in a flow-through cell with a cascade of rotating drums partially filled with conductive particles (called the vertically moving particle bed). Copper deposition from an acidic sodium sulphate solution was used as the model reaction. To evaluate the experimental data a macrohomogeneous mathematical model of potential and current density distribution inside the cell was developed. The electrolyte flow distribution between the empty space above the particle bed and through the bed was evaluated. On the basis of these results the following correlation is proposed:

Two New Organic–Inorganic Hybrids Based on [SiW12O40]4? Anion: Hydrothermal Syntheses, Crystal Structures, and Electrochemical Properties

Two new organic–inorganic hybrid compounds [\textCu^\textI ( \texten ) ₂ ( \textH ₂ \textO )] ₂ { ( \textSiW^\textVI _{1 1} \textW^\textV ₁\textO ₄₀ ) ₂ [ \textCu^\textII ( \texten ) ₂ ( \textH ₂ \textO )] ₂ [\textCu^\textII ( \texten ) ₂ ] ₂ }·6 \textH ₂ \textO [{\text{Cu}}^{\text{I}} \left( {\text{en}} \right)_{ 2} \left( {{\text{H}}_{ 2} {\text{O}}} \right)]_{ 2} \left\{ {\left( {{\text{SiW}}^{\text{VI}}_{ 1 1} {\text{W}}^{\text{V}}_{ 1}{\text{O}}_{ 40} } \right)_{ 2} \left[ {{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{ 2} \left( {{\text{H}}_{ 2} {\text{O}}} \right)\left] {_{ 2} } \right[{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{ 2} } \right]_{ 2} } \right\}{\cdot}6 {\text{H}}_{ 2} {\text{O}} (1) and (H₂ L)₂[SiW₁₂O₄₀]·H₂O (2) [en = ethylenediamine, L = 1,4-bis(3-pyridinecarboxamido)benzene], have been hydrothermally synthesized and characterized by IR, elemental analyses, TG analysis, and single-crystal X-ray diffraction. Structural analyses indicate that compound 1 exhibits an interesting three-dimensional(3D) cross-like supramolecular network through arrangement of a 1D organic–inorganic hybrid chain { ( \textSiW^\textVI _{1 1} \textW^\textV ₁ \textO ₄₀ ) ₂ [ \textCu^\textII ( \texten ) ₂ ( \textH ₂ \textO )] ₂ [\textCu^\textII ( \texten ) ₂ ] ₂ } ^2- . \left\{ {\left( {{\text{SiW}}^{\text{VI}}_{ 1 1} {\text{W}}^{\text{V}}_{ 1} {\text{O}}_{ 40} } \right)_{ 2} \left[ {{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{ 2} \left( {{\text{H}}_{ 2} {\text{O}}} \right)\left] {_{ 2} } \right[{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{ 2} } \right]_{ 2} } \right\}^{ 2- } . The compound 2 consists of protonated L ligand and [SiW₁₂O₄₀]⁴⁻ anion. The protonated L ligands have been extended into a 2D network via hydrogen-bonding interactions. The guest [SiW₁₂O₄₀]⁴⁻ clusters have been incorporated into the square voids of the 2D host network as templates. The electrochemical behavior and electrocatalysis of compound 2 bulk-modified carbon paste electrode (2-CPE) have been studied.     

Electrical resistivity of layers consisting of large carbon particles as a function of the granulometric composition and applied pressure

A mathematical formula is derived for the electrical resistivity ρ′_s of layers of conducting disperse materials as a function of the particle size d and applied pressure P

Structure and Spectral Characteristics of 3D-Supramolecular Coordination Polymers Based on Copper Cyanide and Dimethylquinoxaline

The reactions of K₃[Cu(CN)₄], R₃SnCl (R = Me or ph) and 2,3-dimethyl quinoxaline (dmqox) in H₂O/acetonitrile media at room temperature afford the 3D-supramolecular coordination polymers (SCP) ³_￥ [ \textCu ₂ ( \textCN ) ₂ \textdmqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 2} {\text{dmqox}}} \right] , 1 and ³_￥ [ \textCu ₂ ( \textCN ) ₄ ·( \textPh ₃ \textSn ) ₂ ·\textdmqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 4} \cdot \left( {{\text{Ph}}_{ 3} {\text{Sn}}} \right)_{ 2} \cdot {\text{dmqox}}} \right] , 2. The structure of the tin free 1 consists of parallel zigzag chains connected by dmqox to form 2D-sheets containing hexagonal 18-atom fused Cu₆(CN)₄(dmqox)₂ rings. The interwoven sheets along the a axis are close packed by extensive H-bonds developing 3D-network structure. The structures of 1 and 2 are investigated by elemental analysis IR, NMR and mass spectra. The ESI⁺ and ESI⁻ mass spectra of 2 support its polymeric nature while the ESI⁺ mass spectrum confirms the expected M. W. suggested by elemental analysis. The ¹³C-NMR spectrum of 2 supports the fact that the network structure of 2 contains the rhombic [Cu₂(μ₃-CN)₂] motif. The structure of 2 was compared with the structure of the reported prototype ³_￥ [ \textCu ₂ ( \textCN ) ₄ ·( \textPh ₃ \textSn ) ₂ ·\textqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 4} \cdot \left( {{\text{Ph}}_{ 3} {\text{Sn}}} \right)_{ 2} \cdot {\text{qox}}} \right] as well as the other related structures.     

On the use of pressure‐volume‐temperature data of polyethylene liquids for the determination of their solubility and interaction parameters

Specific volumes of high‐density and low‐density polyethylene liquids at several elevated temperatures and pressures were measured. The measured specific volumes were then used to estimate the thermal expansion coefficients $\left( {{\rm \alpha = }\frac{{\rm 1}}{v}\left( {\frac{{\partial v}}{{\partial T}}} \right)_P } \right)$ and isothermal compressibility $\left( {{\rm \beta = } - \frac{{\rm 1}}{v}\left( {\frac{{\partial v}}{{\partial P}}} \right)_T } \right)$ of the polymers. Two different approaches were used in which one was simply to fit the raw data by second order polynomials to obtain (?v/?T)_P and (?v/?P)_T, while the other by the Sanchez‐Lacombe (S‐L) equation of state. It was found that the resultant α and β obtained from the above methods differ significantly, indicating that the S‐L equation of state may not be suitable for determining α and β at elevated temperatures. When these two sets of α and β were used to calculate the corresponding solubility parameters and then the Flory‐Huggins interaction parameters (χ) of the polymers, the results also differ considerably. Nonetheless, χ obtained from the first method agrees well with the results obtained from small angle neutron scattering measurements while the S‐L equation of state method does not. The current results suggest that solubility and interaction parameters obtained from pressure‐volume‐temperature experiments depend critically on the manner by which the data analysis is performed. Polym. Eng. Sci. 44:853–860, 2004. © 2004 Society of Plastics Engineers.     

Electrochemical behaviour of a new triiron-substituted polyoxomolybdate

A new complex of the Keggin trilacunary polyoxomolybdate (PMo₉) with Fe³⁺ ions, having the formula (PFe₃Mo₉), has been synthesized and characterized by chemical analysis, FT-IR, Raman, UV-VIS-NIR and EPR spectroscopy, as well as by magnetic susceptibility measurements. Cyclic voltammetry performed at different scan rates, pH and supporting electrolyte composition, was used to investigate the electrochemical behaviour of the PFe₃Mo₉ complex in acidic medium and its electrocatalytic effect on H₂O₂ reduction. The voltammetric waves were assigned, and the enhanced electrocatalytic efficiency of PFe₃Mo₉ relative to PMo₉ was attributed to the presence of Fe atoms.