The transition of three types of three-phase behavior in a temperature-composition space of water/C12EO6/propanol/heptane system

 The change of three-phase behavior of a water/hexaethylene-glycol dodecyl ether (C₁₂EO₆)/propanol/heptane system was studied with increasing temperature (30.0–48.9 °C). A cone-like three-phase body consisting of aqueous (W), surfactant (D_p), and oil (O) phases is formed in the composition tetrahedron at lower temperatures. The body is expanded with increasing temperature, and touches the water–C₁₂EO₆–heptane triangle (the base) at 44.8 °C. At about 45.6 °C the loci of the D_p and O phases meet and cut off at a critical double end point and the three-phase body separates into two bodies: one has a chiral shape and the other is unclosed. The unclosed body is transformed with the change of shape of the tie triangle on the base as temperature increases and leaves from the base at 48.9 °C. A closed-loop miscibility gap between middle surfactant (D^′ _p) and O phases or a cone-like three-phase body is formed inside the composition tetrahedron at higher temperatures. The roles of C₁₂EO₆ and propanol are also discussed. Received: 14 April 1998 Accepted: 15 July 1998     

Origins of two surfactant phases (D and Dp′) in a temperature-composition space of water/C12EO6 / propanol / heptane system: tricritical point and critical double end point

The origins of middle surfactant phases (D and Dp′) were investigated in the composition-temperature (49–73 °C) space of a water/hexaethyleneglycol dodecyl ether (C₁₂EO₆)/propanol/heptane system at atmospheric pressure. Two types of three-phase bodies exist in the dilute C₁₂EO₆ region of the four-component composition tetrahedron at 49.0 °C. A cone-like three-phase body consisting of aqueous (W), Dp′, and oil (O) phases becomes thinner with increasing temperature, and collapses into the superimposed critical tie lines (CTL) at 51.7 °C. One end of the superimposed CTL is a critical double end point where the closed-loop coexistence curve of the Dp′ and O phases disappears. The chiral three-phase body consisting of W, D, and O phases shrinks with increasing temperature, and finally vanishes at the tricritical point near 72.5 °C. The roles of C₁₂EO₆ and propanol are discussed and the conditions for the middle surfactant phases are discussed on the basis of the whole series of three-phase behavior. Received: 9 July 1998 Accepted in revised form: 25 August 1998     

Preparation and Crystal Structure of K2Ag12Te7

 Single crystals of K₂Ag₁₂Te₇ (a = 11.460(2), c = 4.660(1) ?; V = 530.01 ?³; space group: P6₃/m; Z = 1) were synthesized under hydrothermal conditions at 250°C in concentrated aqueous KOH solution from elementary silver and tellurium. The crystal structure is characterized by trigonal prismatic KTe₆ polyhedra, connected via two common faces to KTe₃ rods parallel to [001]. These rods are combined by two crystallographically independent Ag atoms, each coordinated to four Te and three Ag atoms (Ag–Te and Ag–Ag < 3.1 ?) to a framework of the formula (K₂Ag₁₂Te₆)^2 + and with channels parallel to the sixfold axis. These channels are statistically occupied by one further Te atom per unit cell, distributed over two independent positions.     

Oil-Induced Structural Change in Nonionic Microemulsions

Effect of added oil (heptane or squalane) on the microemulsion structures in polyoxyethylene dodecyl ether (C₁₂EO_n) systems was investigated by means of phase behavior and NMR diffusion experiments. In the binary water-C₁₂EO_n systems, an isotropic fluid, D₂ (or L₃), and an aqueous micellar solution, Wm, phases are successively formed with increasing the EO-chain length. Upon addition of heptane, D₂ and Wm phases are merged and a microemulsion of large solubilization is produced at a low surfactant concentration. With squalane, the solubilization of oil in D₂ phase is very low or almost zero, whereas the oil solubilization in Wm phase is relatively large. These structural changes in microemulsions are discussed based on the self-diffusion coefficients of water, oil, and surfactant measured by the PGSE-NMR method. The difference in the phase behavior may be attributed to the difference in the penetration tendency of oil in the surfactant palisade layer.     

Physicochemical characterization of a novel surfactant peptide containing an arginine cation and laurate anion

 A novel surfactant peptide consisting of an arginine cation with laurate anion has been synthesized, purified and characterized. The critical micellar concentration (cmc) of peptide in aqueous solutions has been determined using spectroscopic techniques and is found to increase from 0.06 to 0.11 mM with increasing temperature (15–45 °C). Cmc is also determined in the presence of salts like NaCl, KCl and sodium acetate and it is found that these electrolytes hinder aggregation with a significant increase in the case of sodium acetate. The aggregation number of the surfactant peptide has been determined using fluorescence quenching measurements and is observed to decrease from 14 to 6 with increasing temperature (15–45 °C). The standard free energy change (ΔG ⁰ _m) and standard enthalpy change (ΔH ⁰ _m) of the peptide aggregate are found to be negative with a small positive value for standard entropy change (ΔS ⁰ _m). The peptide aggregate seems to undergo phase transition above 50 °C as observed from UV–vis and fluorescence spectroscopy. From pyrene binding studies, it is shown that the interior dielectric constant increases from 5.08 at 34 °C to 8.77 at 50 °C and further decreases with increase in temperature indicating a phase change at 50 °C. Also, the ratio of excimer intensity to monomer intensity, which is a measure of microviscosity of the aggregate, decreases with increase in temperature with a change at 50 °C indicating a phase change. Received: 14 February 1997 Accepted: 13 August 1997     

Conformation of poly(L-glutamic acid) in aqueous solutions of linear amphiphiles with a cationic group at both ends

The conformations of poly(l-glutamic acid) [P(Glu)] in solutions of the bipolar amphiphile 1,20-icosanediylbis(alkylammonium chloride) [C20(RA)₂], where RA includes trimethylammonium (TMA), dimethylammonium (DMA), or methylammonium (MA), were investigated with measurements of the circular dichroism spectra at 10–35 °C. All C20(RA)₂ induced an α-helix of P(Glu) in the aqueous solutions. The residue molar ellipticity at 222 nm showed a similar dependence on the amphiphile concentration (C _s) below 0.5 of the ratio of 2C _s to the residue concentration (C _p) of P(Glu), but it separated into three directions at 2C _s/C _p>0.5. C20(MA)₂ induced an α-helix of P(Glu) at 2C _s/C _p<0.5 followed by a helix aggregate at 2C _s/C _p>0.5. C20(DMA)₂ and C20(TMA)₂ also induced an α-helix, but a helix aggregate. C20(TMA)₂ indicated a strong temperature dependence and did not induce a complete α-helix at 35 °C. Received: 20 June 2001 Accepted: 6 September 2001     

Raman Spectra of Tungsten-Bearing Solutions

Raman spectroscopy at 25 °C was performed to analyze speciation in quenched solutions after experiments on sodium tungstates and sodium tungstate bronze dissolution at t=500 °C, p=1000 bar. The experiments were conducted under different oxidation-reduction conditions in sodium chloride solution media. The spectra of the quenched solutions were different from those of the reference solutions of 0.02 mol⋅kg⁻¹ W(VI) (H₂O) in the pH range 2.3–7.2. Thermodynamic models were established and the fields of predominance of different isopolytungstate species at 25–50 °C were determined. The experimental results of tungstate dissolution demonstrates that reduced tungstate solutions may contain a significant amount of tungsten species with valence states lower than W(VI).     

Spin Crossover Properties of the [Fe( PM - BiA )2(NCS)2] Complex – Phases I and II

Summary.  In the present review, we reexamine the photomagnetic properties of the [Fe(PM-BiA)₂(NCS)₂], cis-bis(thiocyanato)-bis[(N-2′-pyridylmethylene)-4-(aminobiphenyl)]iron(II), compound which exhibits, depending on the synthetic method, an exceptionally abrupt spin transition (phase I) with a very narrow hysteresis (T _1/2↓ = 168 K and T _1/2↑ = 173 K) or a gradual spin conversion (phase II) occurring at 190 K. In both cases, light irradiation in the tail of the ¹MLCT-LS absorption band, at 830 nm, results in the population of the high-spin state according to the light-induced excited spin-state trapping (LIESST) effect. The capacity of a compound to retain the light-induced HS information, estimated through the T(LIESST) experiment, is determined for both phases. Interestingly, the shape of the T(LIESST) curve is more gradual for the phase II than for the phase I and the T(LIESST) value is found considerably lower in the case of the phase II. The kinetics parameters involved in the photoinduced high-spin→low-spin relaxation process are estimated for both phases. From these data, the experimental T(LIESST) curves are simulated and the particular influence of the cooperativity as well as of the parameters involved in the thermally activated and tunneling regions are discussed. The Light-Induced Thermal Hysteresis (LITH), originally described for the strongly cooperative phase I, is also reinvestigated. The quasi-static LITH loop is determined by recording the photostationary points in the warming and cooling branches. Corresponding authors. E-mail: letard@icmcb.u-bordeaux.fr Received August 26, 2002; accepted August 30, 2002     

Oxygen deficiency and phase transitions in SrCo1– x – y Fe x Cr y O3–δ ( x =0.10–0.40, y =0–0.05)

Oxygen-deficient phases based on perovskite-like strontium cobaltites-ferrites are promising mixed conductors for high-temperature electrochemical applications. The p(O₂)-T-δ diagrams for the oxide systems SrCo_{1– x – y} Fe _x Cr _y O_{3– δ} (x=0.10–0.40; y=0–0.05) were studied at 500–1000 °C in the oxygen pressure range from 10^–5 to 0.21 atm using the coulometric titration technique and thermogravimetric analysis. Stability limits of the cubic perovskite phases having a high oxygen ionic conductivity were evaluated as functions of temperature, oxygen partial pressure and oxygen nonstoichiometry. It was found that doping with chromium and increasing the iron content in SrCo(Fe,Cr)O_{3– δ} both lead to a considerable enlargement of the cubic perovskite phase existence domain towards lower temperatures and reduced oxygen pressures. Electronic Publication     

Preparation and Crystal Structure of K2Ag12Te7

Summary.  Single crystals of K₂Ag₁₂Te₇ (a = 11.460(2), c = 4.660(1) ?; V = 530.01 ?³; space group: P6₃/m; Z = 1) were synthesized under hydrothermal conditions at 250°C in concentrated aqueous KOH solution from elementary silver and tellurium. The crystal structure is characterized by trigonal prismatic KTe₆ polyhedra, connected via two common faces to KTe₃ rods parallel to [001]. These rods are combined by two crystallographically independent Ag atoms, each coordinated to four Te and three Ag atoms (Ag–Te and Ag–Ag < 3.1 ?) to a framework of the formula (K₂Ag₁₂Te₆)^2 + and with channels parallel to the sixfold axis. These channels are statistically occupied by one further Te atom per unit cell, distributed over two independent positions. Received May 17, 2001. Accepted (revised) July 3, 2001     

Crystalline phase content and ionic conductivity correlation in LATP glass–ceramic

Li₂O–Al₂O₃–TiO₂–P₂O₅ (LATP) glass was fabricated by conventional melt quenching route. Glass transition temperature (T _g = 296 °C) and crystallization temperatures (T _C1,2) were obtained from thermal analysis. LATP glass was converted to glass–ceramic by heat treatment in the range 550–950 °C for 6 h. X-ray diffraction analysis revealed LiTi₂(PO₄)₃ as a major phase. Ionic conductivity increased monotonically with concentration, reaching a maximum of ~10⁻⁴ S/cm. AlPO₄ phase was detected in samples heat-treated above 850 °C. Its presence decreased the conductivity, suggesting LiTi₂(PO₄)₃ phase as main contributor to high ionic conductivity. NMR spectra confirmed the presence of mobile ⁷Li ions in the entire sample series and also gave some information on the structure and dynamics of conductivity.     

Chromium(III) Hydroxide Solubility in the Aqueous K+-H+-OH?-CO2-HCO 3? -CO 32? -H2O System: A?Thermodynamic Model

Chromium(III)-carbonate reactions are expected to be important in managing high-level radioactive wastes. Extensive studies on the solubility of amorphous Cr(III) hydroxide solid in a wide range of pH (3–13) at two different fixed partial pressures of CO₂(g) (0.003 or 0.03 atm.), and as functions of K₂CO₃ concentrations (0.01 to 5.8 mol⋅kg⁻¹) in the presence of 0.01 mol⋅dm⁻³ KOH and KHCO₃ concentrations (0.001 to 0.826 mol⋅kg⁻¹) at room temperature (22±2 °C) were carried out to obtain reliable thermodynamic data for important Cr(III)-carbonate reactions. A combination of techniques (XRD, XANES, EXAFS, UV-Vis-NIR spectroscopy, thermodynamic analyses of solubility data, and quantum mechanical calculations) was used to characterize the solid and aqueous species. The Pitzer ion-interaction approach was used to interpret the solubility data. Only two aqueous species [Cr(OH)(CO₃)₂²⁻ and Cr(OH)₄CO₃³⁻] are required to explain Cr(III)-carbonate reactions in a wide range of pH, CO₂(g) partial pressures, and bicarbonate and carbonate concentrations. Calculations based on density functional theory support the existence of these species. The log ₁₀ K° values of reactions involving these species [{Cr(OH)₃(am) + 2CO₂(g)⇌Cr(OH)(CO₃)₂²⁻+2H⁺} and {Cr(OH)₃(am) + OH⁻+CO₃²⁻ ⇌Cr(OH)₄CO₃³⁻}] were found to be −(19.07±0.41) and −(4.19±0.19), respectively. No other data on any Cr(III)-carbonato complexes are available for comparisons.     

Hydrate formation in the tetraethylammonium hydroxide-water system

A phase diagram of the tetraethylammonium hydroxide-water binary system was studied by differential thermal analysis. Seven crystal phases of tetraethylammonium hydroxide were found. Two of them are stable: tetrahydrate (T _m = 47.0°C), two phases of a compound with the hydration number 7.5 (T _m = −18.1 and −23.2°C); five are metastable phases: two polymorphs of pentahydrate (T _m = 39.4 and 0.9°C), hexahydrate (T _m = −70.1°C), and a compound with hydrate number 10–11 (T _m = −112°C).     

Cathodoluminescence Depth Profiling in SiO2:Ge Layers

 For investigation of the luminescent center profile cathodoluminescence measurements are used under variation of the primary electron energy E ₀ = 2…30 keV. Applying a constant incident power regime (E ₀·I ₀ = const), the depth profiles of luminescent centers are deduced from the range of the electron energy transfer profiles dE/dx. Thermally grown SiO₂ layers of thickness d = 500 nm have been implanted by Ge⁺-ions of energy 350 keV and doses (0.5–5)10¹⁶ ions/cm². Thus Ge profiles with a concentration maximum of (0.4 – 4) at% at the depth of d_m≅240 nm are expected. Afterwards the layers have been partially annealed up to T _a = 1100 °C for one hour in dry nitrogen. After thermal annealing, not only the typical violet luminescence (λ = 400 nm) of the Ge centers is strongly increased but also the luminescent center profiles are shifted from about 250 nm to 170 nm depth towards the surface. This process should be described by Ge diffusion processes, precipitation and finally Ge nanocluster formation. Additionally, a Ge surface layer is piled-up extending to a depth of roughly 25 nm.     

Electrochemistry and electrocatalytic activity of polypyrrole/ferrocyanide films on a glassy carbon electrode

Functionalized polypyrrole films were prepared by incorporation of Fe(CN)₆ ³⁻ as doping anion during the electropolymerization of pyrrole at a glassy carbon electrode from aqueous solution. The electrochemical behavior of the Fe(CN)₆ ³⁻/Fe(CN)₆ ⁴⁻ redox couple in polypyrrole was studied by cyclic voltammetry. An obvious surface redox reaction was observed and dependence of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole film with ferrocyanide incorporated was demonstrated by oxidation of ascorbic acid at the optimized pH of 4 in a glycine buffer. The catalytic effect for mediated oxidation of ascorbic acid was 300 mV and the bimolecular rate constant determined for surface coverage of 4.5 × 10⁻⁸ M cm⁻² using rotating disk electrode voltammetry was 86 M⁻¹ s⁻¹. Furthermore, the catalytic oxidation current was linearly dependent on ascorbic acid concentration in the range 5 × 10⁻⁴–1.6 × 10⁻² M with a correlation coefficient of 0.996. The plot of i _p versus v ^1/2 confirms the diffusion nature of the peak current i _p. Received: 12 April 1999 / Accepted: 25 May 1999     

Development of a reference solution for the pH of seawater

A method that uses a Harned cell to perform potentiometric pH measurements has been optimized and applied to an aqueous solution of simulated seawater that contains sodium perchlorate, sodium sulfate, sodium hydrogen carbonate and boric acid and has an ionic strength I of 0.57 mol kg⁻¹. The standard metrological approach developed for the measurement of pH in low ionic strength aqueous solutions was maintained, but a few modifications were necessary, and measurement procedures and calculations were modified ad hoc from those adopted in conventional protocols. When determining the standard potential of the cell, E°, NaClO₄ salt was added to a 0.01 mol/kg HCl solution to attain the same ionic strength as the test solution and to investigate possible specific effects related to the high levels and the nature of the background electrolyte. An appropriate value of γ _±HCl (0.737) was then selected from the literature, based on a realistic value for I. Finally, in order to convert the acidity function at zero chloride molality into pH, a suitable value of γ _Cl (0.929) was calculated. As a result, we obtained pH = 8.18 (T = 25 °C) with an associated expanded uncertainty U = 0.01 (coverage factor k = 2). The aim was to establish a sound basis for the pH measurement of seawater by identifying the critical points of the experimental and theoretical procedure, and to discuss further possible developments that would be useful for achieving a reference solution.     

Cage Structure Formation of Singly Doped Aluminum Cluster Cations Al<Subscript><Emphasis Type="BoldItalic">n</Emphasis></Subscript><Emphasis Type="BoldItalic">TM</Emphasis><Superscript>+</Superscript> (<Emphasis Type="BoldItalic">TM</Emphasis> = Ti,V, Cr)

Structural information on free transition metal doped aluminum clusters, Al _n TM ⁺ (TM = Ti, V, Cr), was obtained by studying their ability for argon physisorption. Systematic size (n = 5 – 35) and temperature (T = 145 – 300 K) dependent investigations reveal that bare Al _n ⁺ clusters are inert toward argon, while Al _n TM ⁺ clusters attach one argon atom up to a critical cluster size. This size is interpreted as the geometrical transition from surface-located dopant atoms to endohedrally doped aluminum clusters with the transition metal atom residing in an aluminum cage. The critical size, n _crit , is found to be surprisingly large, namely n _crit = 16 and n _crit = 19 – 21 for TM = V, Cr, and TM = Ti, respectively. Experimental cluster–argon bond dissociation energies have been derived as function of cluster size from equilibrium mass spectra and are in the 0.1–0.3 eV range.     

The parathiocyanogen electrode

Stable, yellow anodic films of parathiocyanogen (SCN) _x were formed on a platinum electrode from 2.8 M KSCN in methanol at 45 °C at a constant current of 20–40 mA cm⁻² for 15–30 min. Loosely bound orange crystals of a more amorphous character were removed by rinsing to leave an adherent yellow film with sharp Raman bands under 647.1 nm laser excitation at 627 cm⁻¹ (vCS), 1152 cm⁻¹ and 1236–1261 cm⁻¹ (vNN and vCN). The lack of electroactivity and short-lived photocurrents pointed to an insulating film at potentials up to 1.0 V (SHE). At more positive potentials, longer-lasting photocurrents were obtained, consistent with breakdown of the insulating film. XPS scans confirmed N:C:S ratios close to 1:1:1, with a deficiency of S of some 10% due to S lost as sulfate at the film surface. Oxidation of SeCN⁻ in neutral aqueous solution led to the formation of a less-stable orange paraselenocyanogen film with a Raman band at 1256–1267 cm⁻¹, which decomposed within a day to grey selenium. Received: 12 December 1997 / Accepted: 23 March 1998     

Study of Nd2–x Ce x CuO4?±?δ (x?=?0.1–0.25) as cathode material for intermediate-temperature solid oxide fuel cells

The solid solubility limit of Ce in Nd_2–x Ce _x CuO_4 ± δ , prepared by sol–gel process, is established up to x = 0.2. The transition from negative temperature coefficient to positive temperature coefficient, within the solid solubility region, is observed at 620 °C. The area-specific-resistance (ASR) is optimized for electrochemical cell sintered at 800 °C. ASR enhances with increase in sintering temperature of cell. ASR value of 0.93 ohm cm² at 700 °C, determined by electrochemical impedance spectroscopy is comparable against that by voltage versus current (V–I) characteristics at 0.98 ohm cm² at the same temperature. Electrochemical performance and ASR of Nd_1.8Ce_0.2CuO_4 ± δ is improved when prepared by sol–gel route over solid-state reaction, which is attributed to uniform size and shape of nanocrystalline grains.     

DODAB and DODAC bilayer-like aggregates in the micromolar surfactant concentration domain

In the millimolar concentration domain (typically 1 mM), dioctadecyldimethylammonium bromide and chloride (DODAX, X representing Br⁻ or Cl⁻ counterions) molecules assemble in water as large unilamellar vesicles. Differential-scanning calorimetry (DSC) is a suitable technique to obtain the melting temperature (T _m) characteristic of surfactant bilayers, while fluorescence spectroscopy detects formation of surfactant aggregates, like bilayers. These two techniques were combined to investigate the assembly of DODAX molecules at micromolar concentrations, from 10 to 100 μM. At 1 mM surfactant, T _m ≈ 45 °C and 49 °C, respectively, for DODAB and DODAC. DSC and fluorescence of Nile Red were used to show the formation of DODAX aggregates, at the surfactant concentration as low as 10 μM, whose T _m decreases monotonically with increasing DODAX concentration to attain the value for the ordinary vesicles. The data indicate that these aggregates are organized as bilayer-like structures.