A new ion-selective electrode based on aluminium tungstate for Fe(III) determination in rock sample, pharmaceutical sample and water sample

An inorganic cation exchanger, aluminum tungstate (AT), has been synthesized by adding 0·1 M sodium tungstate gradually into 0·1 M aluminium nitrate at pH 1·2 with continuous stirring. The ion exchange capacity for Na⁺ ion and distribution coefficients of various metal ions was determined on the column of aluminium tungstate. The distribution studies of various metal ions showed the selectivity of Fe(III) ions by this cation exchange material. So, a Fe(III) ion-selective membrane electrode was prepared by using this cation exchange material as an electroactive material. The effect of plasticizers viz. dibutyl phthalate (DBP), dioctylphthalate (DOP), di-(butyl) butyl phosphate (DBBP) and tris-(2-ethylhexylphosphate) (TEHP), has also been studied on the performance of membrane sensor. It was observed that the membrane containing the composition AT: PVC: DBP in the ratio 2: 20: 15 displayed a useful analytical response with excellent reproducibility, low detection limit, wide working pH range (1–3·5), quick response time (15 s) and applicability over a wide concentration range of Fe(III) ions from 1 × 10⁻⁷ M to 1 × 10⁻¹ M with a slope of 20 ± 1 mV per decade. The selectivity coefficients were determined by the mixed solution method and revealed that the electrode was selective for Fe(III) ions in the presence of interfering ions. The electrode was used for atleast 5 months without any considerable divergence in response characteristics. The constructed sensor was used as indicator electrode in the potentiometric titration of Fe(III) ions against EDTA and Fe(III) determination in rock sample, pharmaceutical sample and water sample. The results are found to be in good agreement with those obtained by using conventional methods.     

Synthesis and electrochemical application of carbon nanotubes obtained from hexachloroethane

Carbon nanotubes (CNTs) with the average inner (outer) diameter of 10–20 nm (20–40 nm) and length up to 100s of nanometers were synthesized via Wurtz reaction at 400 °C for 12 h, using C₂Cl₆ and Na as reactants. These CNTs, having more defects because of the sp³ bonding raw material of C₂Cl₆, were used as electrode material to detect dopamine (DA) via cyclic voltammetry. The results show that there exists linear relation between peak currents and DA concentration in the range of 2 × 10⁻⁷∼2.8 × 10⁻⁴ mol L⁻¹.The linear regression equation is expressed as Ip (μA) = 0.089 + 0.134c (μmol L⁻¹). This CNTs-modified electrode showed high sensitivity with detection limit of 1 × 10⁻⁷ mol L⁻¹.     

Pressure-induced band cross-over in Pb1−x Sn x Te

Resistivity and thermoelectric power studies have been carried out on two semiconductor alloy systems viz Pb_0·8Sn_0·2Te and Pb_0·6Sn_0·4Te up to 35 kbar pressure. Thermoelectric power and resistivity data on Pb_0·8Sn_0·2Te indicate that the energy gapE _g=E _{L −} ⁶ −E _{L 6} ⁺ decreases with pressure resulting in a zero gap state near 35 kbar pressure. TEP studies on the alloy system Pb_0·6Sn_0·4Te provide direct evidence for a pressure induced L ₆ ⁻ →L ₆ ⁺ cross over transition.     

A Study of Specific Heat Capacity Functions of Polyvinyl Alcohol–<Emphasis Type="Italic">Cassava</Emphasis> Starch Blends

The specific heat capacity (C _sp) of polyvinyl alcohol (PVOH) blends with cassava starch (CSS) was studied by the differential scanning calorimetry method. Specimens of PVOH–CSS blends: PPV37 (70 mass% CSS) and PPV46 (60 mass% CSS) were prepared by a melt blending method with glycerol added as a plasticizer. The results showed that the specific heat capacity of PPV37 and PPV46 at temperatures from 330 K to 530 K increased from (2.963 to 14.995)  J· g⁻¹ · K⁻¹ and (2.517 to 14.727)  J · g⁻¹· K⁻¹, respectively. The specific heat capacity of PVOH–CSS depends on the amount of starch. The specific heat capacity of the specimens can be approximated by polynomial equations with a curve fitting regression > 0.992. For instance, the specific heat capacity (in J · g⁻¹ · K⁻¹) of PPV37 can be expressed by C _sp = −17.824 + 0.063T and PPV46 by C _sp = −18.047 + 0.061T, where T is the temperature (in K).     

Potentiodynamical deposition of nanosized manganese oxides as high capacitance electrochemical capacitors

Nanosized manganese oxides powders were potentiodynamically deposition onto the Pb substrates by anodic oxidation in 0.5 mol L⁻¹ MnSO₄ and 0.5 mol L⁻¹ H₂SO₄ mixed solution at 40 °C. The chemical composition of the sample was determined by complex titration with ethylene diamine tetraacetic acid and redox titration. X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and chronopotentiometry were employed to characterize the materials. The highest specific capacitance of the MnO_x composite electrode was up to 420 F g⁻¹ in 1.0 mol L⁻¹ Na₂SO₄ electrolyte at the scan rate 5 mV s⁻¹. The synthesized nanosized manganese oxide exhibited ideal capacitive behavior indicating a promising electrode material for electrochemical supercapacitors.     

Effect of cobalt substitution on magnetic and transport properties of Nd0·5Sr0·5Mn1?xCoxO3 (x = 0·1, 0·3 and 0·5)

The magnetic and transport properties of the compounds Nd_0·5Sr_0·5Mn_1-x_{{\rm 1}-{x}}Co_x_{{x}}O₃ (x = 0·1, 0·3 and 0·5), synthesized by citrate–gel route have been investigated. The spin transition in cobaltates at low temperatures affects the magnetic as well as transport properties. The irreversibility behaviour between the zero-field cooled (ZFC) and field cooled (FC) magnetization as a function of temperature becomes stronger with increasing Co content. This is understood on the basis of glassy behaviour, which becomes more robust with increasing Co substitution. The non-saturating M–H behaviour indicates strong magnetic inhomogeneities which may cause the magnetic phase separation at the nanoscopic length scale. The double exchange interaction is stronger between Mn^3 +–O^2 −–Mn^4 + as compared to Co^3 +–O^2 −–Co^4 + pairs. Co-substitution suppresses the double exchange which will lead to cluster/spin glass like behaviour as well as semiconducting features due to localization of charge carriers (mobile e_g{e}_{\rm g} electrons).     

Distillation Separation of Hydrofluoric Acid and Nitric Acid from Acid Waste Using the Salt Effect on Vapor–Liquid Equilibrium

This study presents the distillation separation of hydrofluoric acid with use of the salt effect on the vapor–liquid equilibrium for acid aqueous solutions and acid mixtures. The vapor–liquid equilibrium of hydrofluoric acid + salt systems (fluorite, potassium nitrate, cesium nitrate) was measured using an apparatus made of perfluoro alkylvinylether. Cesium nitrate showed a salting-out effect on the vapor–liquid equilibrium of the hydrofluoric acid–water system. Fluorite and potassium nitrate showed a salting-in effect on the hydrofluoric acid–water system. Separation of hydrofluoric acid from an acid mixture containing nitric acid and hydrofluoric acid was tested by the simple distillation treatment using the salt effect of cesium nitrate (45 mass%). An acid mixture of nitric acid (5.0 mol · dm⁻³) and hydrofluoric acid (5.0 mol · dm⁻³) was prepared as a sample solution for distillation tests. The concentration of nitric acid in the first distillate decreased from 5.0 mol · dm⁻³ to 1.13 mol · dm⁻³, and the concentration of hydrofluoric acid increased to 5.41 mol · dm⁻³. This first distillate was further distilled without the addition of salt. The concentrations of hydrofluoric acid and nitric acid in the second distillate were 7.21 mol · dm⁻³ and 0.46 mol · dm⁻³, respectively. It was thus found that the salt effect on vapor–liquid equilibrium of acid mixtures was effective for the recycling of acids from acid mixture wastes.     

Synthesis,growth, optical,mechanical and electrical properties of <Emphasis Type="Italic">L</Emphasis>-lysine <Emphasis Type="Italic">L</Emphasis>-lysinium dichloride nitrate (<Emphasis Type="Italic">L</Emphasis>-LLDN) single crystal

Semi-organic nonlinear optical material, L-lysine L-lysinium dichloride nitrate (2C₆H₁₅N₂O₂⁺_{2}^{+} · H⁺ · NO₃^-_{3}^{-} · 2Cl⁻) was synthesized at room temperature. Single crystals of L-LLDN were grown by slow cooling solution growth technique. The grown crystal was confirmed by powder X-ray diffraction analysis. The crystalline perfection of the grown single crystal was characterized by high-resolution X-ray diffraction (HRXRD) studies. The cut-off wavelength was determined by UV-vis transmission spectral analysis. The frequency doubling of the grown crystal was confirmed by powder second harmonic generation (SHG) measurement. The refractive index and birefringence of the crystal were determined using He–Ne laser source. Mechanical property of the crystal was determined by Vickers hardness tester. The frequency and temperature dependence of dielectric constant (ε _r), dielectric loss (tan δ) and a.c. conductivity (σ _ac) were also measured.     

Application of photoacoustic and photothermal techniques for heat conduction measurements in a free-standing chemical vapor-deposited diamond film

Heat conduction in a free-standing chemical vapor-deposited polycristalline diamond film has been investigated by means of combined front and rear photoacoustic signal detection techniques and also by means of a “mirage” photothermal beam deflection technique. The results obtained with the different techniques are consistent with a value of α=(5.5±0.4)×10⁻⁴ m² · s⁻¹ for thermal diffusivity, resulting in a value ofκ=(9.8±0.7)×10² W·m⁻¹·K⁻¹ for thermal conductivity when literature values for the density and heat capacity for natural diamond are used.     

Protonic conduction in Al2(SO4)3·16H2O: coulometry,transient ionic current,infrared and electrical conductivity studies

Proton transport in Al₂(SO₄)₃·16H₂O has been established using different techniques namely coulometry, transient ionic current, i.r., DTA/TGA and electrical conductivity. The possible charge carriers are H⁺ and OH⁻ generated as a result of possible electrolysis of hydrate water molecules. The mobilities of the two charge carriers are approximately 4×10⁻⁵ and 2.4×10⁻⁵cm²V⁻¹s⁻¹. The electrical conductivity shows strong dependence upon humidity and also shows a against 1/T behaviour closely related with its thermal dehydration reaction.     

Li-storage and cycling properties of spinel,CdFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as an anode for lithium ion batteries

Cadmium ferrite, CdFe₂O₄, is synthesized by urea combustion method followed by calcination at 900°C and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) techniques. The Li-storage and cycling behaviour are examined by galvanostatic cycling, cyclic voltammetry (CV) and impedance spectroscopy in the voltage range, 0·005–3·0 V vs Li at room temperature. CdFe₂O₄ shows a first cycle reversible capacity of 870 (± 10) mAhg⁻¹ at 0·07C-rate, but the capacity degrades at 4 mAhg⁻¹ per cycle and retains only 680 (± 10) mAhg⁻¹ after 50 cycles. Heat-treated electrode of CdFe₂O₄ (300°C; 12 h, Ar) shows a significantly improved cycling performance under the above cycling conditions and a stable capacity of 810 (± 10) mAhg⁻¹ corresponding to 8·7 moles of Li per mole of CdFe₂O₄ (vs theoretical, 9·0 moles of Li) is maintained up to 60 cycles, with a coulombic efficiency, 96–98%. Rate capability of heat-treated CdFe₂O₄ is also good: reversible capacities of 650 (± 10) and 450 (± 10) mAhg⁻¹ at 0·5 C and 1·4 C (1 C = 840 mAg⁻¹) are observed, respectively. The reasons for the improved cycling performance are discussed. From the CV data in 2–15 cycles, the average discharge potential is measured to be ∼0·9 V, whereas the charge potential is ∼2·1 V. Based on the galvanostatic and CV data, ex situ-XRD, -TEM and -SAED studies, a reaction mechanism is proposed. The impedance parameters as a function of voltage during the 1st cycle have been evaluated and interpreted. Dedicated to Prof. C N R Rao on his 75th birthday, and his contributions to science for the past 56 years     

Physical Properties of AZ91D Measured Using the Draining Crucible Method: Effect of SF<Subscript>6</Subscript>

The draining crucible (DC) technique was used for measurements on AZ91D under Ar and SF₆. The DC technique is a new method developed to simultaneously measure the physical properties of fluids, the density, surface tension, and viscosity. Based on the relationship between the height of a metal in a crucible and the outgoing flow rate, a multi-variable regression is used to calculate the values of these fluid properties. Experiments performed with AZ91D at temperatures from 923 K to 1173 K indicate that under argon, the surface tension (N · m⁻¹) and density (kg · m⁻³) are [0.63 − 2.13 × 10⁻⁴ (T − T _L)] and [1656 − 0.158 (T − T _L)], respectively. The viscosity (Pa · s) has been determined to be [1.455 × 10⁻³ − 1.209 × 10⁻⁵ (T − T _L)] over the temperature range from 921 K to 967 K superheat. Above 967 K, the viscosity of the alloy under argon seems to be constant at (2.66 × 10⁻⁴ ± 8.67 × 10⁻⁵) Pa · s. SF₆ reduces the surface tension of AZ91D.     

The Viscosity of Aqueous Alkali-Chloride Solutions up to 623 K, 1,000 bar,and High Ionic Strength

An accurate viscosity (dynamic viscosity) model is developed for aqueous alkali-chloride solutions of the binary systems, LiCl–H₂O, NaCl–H₂O, and KCl–H₂O, from 273 K to 623 K, and from 1 bar to 1,000 bar and up to high ionic strength. The valid ionic strengths for the LiCl–H₂O, NaCl–H₂O, and KCl–H₂O systems are 0 to 16.7 mol · kg⁻¹, 0 to 6 mol · kg⁻¹, and 0 to 4.5 mol · kg⁻¹, respectively. Comparison of the model with about 4,150 experimental data points concludes that the average absolute viscosity deviation from experimental data in the above range is within or about 1 % for the LiCl–H₂O, NaCl–H₂O, and KCl–H₂O mixtures, indicating the model is of experimental accuracy. With a simple mixing rule, this model can be extrapolated to predict the viscosity of ternary aqueous alkali-chloride solutions, making it useful in reservoir fluid flow simulation. A computer code is developed for this model and can be obtained from the author: (maoshide@cugb.edu.cn).     

Hydrogen-Bonded Structure of 2:1 TCNQ Salt of 2-Methyl-5-Phenyl-7,9-Dichloro-1,6-Diazaphenalene

The crystal structure of 2:1 TCNQ salt of 2-methyl-5-phenyl-7,9-dichloro-1,6-diazaphenalene (1) was investigated for the construction of new hydrogen-bonded charge-transfer complexes. This salt was composed of neutral 1, protonated 1 (1·H ⁺) and ionic TCNQ (TCNQ^{· −}), and constructed a segregated structure with uniform π-stackings. The N–H···N≡C hydrogenbonding between 1/1·H⁺ and TCNQ^{· −} formed the D-A-D triad, and connected the columnar structures.     

Cation-exchange kinetic studies on poly-<Emphasis Type="Italic">o</Emphasis>-toluidine Ce(IV) phosphate: a nano-composite and electrical conducting material

An advanced cation-exchange nano-composite poly-o-toluidine Ce(IV) phosphate was synthesized by sol–gel technique by incorporating Ce(IV) phosphate precipitate with the matrix of poly-o-toluidine. The material showed good ion-exchange behavior and used successfully in separation of metal ions. The conductivity of the composite was found within the range of 10⁻² to 10⁻³ S/cm⁻¹; measured by four-in-line probe DC electrical conductivity measuring technique. The conductivity is at the border of metallic and semiconductor region. Ion-exchange kinetics for few divalent metal ions was evaluated by particle diffusion-controlled ion-exchange phenomenon at four different temperatures. The particle diffusion mechanism is confirmed by the linear τ (dimensionless time parameter) versus t (time) plots. The exchange processes thus controlled by the diffusion within the exchanger particle for the systems studies herein. Some physical parameters like self-diffusion coefficient (D ₀), energy of activation (E _a), and entropy of activation (∆S°) have been evaluated under conditions favoring a particle diffusion-controlled mechanism.     

Preparation and properties of melt-processed thick films of YBCO

A detailed study has been carried out of the successful fabrication of high current capacity, thick films of YBCO on yttria-stabilized zirconia substrates. This has involved the optimization of a number of processing parameters including material composition, processing temperatures and times, ink additives and so on. As a result of this work, thick films have been obtained with thicknesses of as little as 7μ, which are superconducting withT _c=91·5 K and have critical current densities at 77 K of almost 3×10³ Acm⁻². This current decreases rapidly with increasing magnetic field strength, reaching an almost constant value of 100–200 Acm⁻² at 0·4 T.     

Physical Properties of Pyridinium Fluorohydrogenate, [pyridine · H+][H2F3]−

Ionic liquids (ILs), also referred to as molten salts, have found application as electrolytes for batteries and super-capacitors, in electroplating baths, as designer solvents, and as reaction media. A few of the desired properties of a super-capacitor electrolyte are nonflammability, thermal stability, and electrochemical stability. ILs containing aromatic cations have been shown to have low viscosity which results in a high electrochemical conductivity. There is a delicate balance between increasing the thermal stability, or decreasing the melting point, and increasing the electrochemical conductivity of the IL. This study focuses on pyridinium fluorohydrogenate, [pyridine · H⁺][H₂F₃]⁻. Pyridinium fluorohydrogenate has been synthesized by the reaction of pyridine and anhydrous hydrofluoric acid. This IL has a relatively high electrical conductivity (~98 mS · cm⁻¹ at 23 °C), a wide electrochemical window, and a boiling point of 186 °C. A stable gel can also be formed by combining [pyridine · H⁺][H₂F₃]⁻ and a super absorbent polymer such as polyacrylic acid. The gel adds mechanical stability to the matrix while not greatly affecting the conductivity of the IL.     

Iron-based composite oxides as alternative negative electrodes for lithium-ion batteries

Nanosized lithiated iron oxides with 10 and 50 wt.% SiO₂ were prepared by a sol–gel method using 1 M Fe(NO₃)₃ · 9H₂O and 1 M LiNO₃ aqueous solutions in a stoichiometric ratio of 1:1 and colloidal silica. Dried xerogel was calcinated at 700 °C for 4 h in air. The X-ray data of samples synthesized using 10% and 50% SiO₂ showed the presence of a mixture of two phases: α-LiFeO₂ and Li_1−x Fe₅O₈ (0 < x ≤ 0.1) for a sample containing 10% SiO₂ and LiFe(SiO₃)₂ and Fe₂O₃ (h) for a sample with 50% SiO₂. The electrochemical behaviour of the compounds was investigated galvanostatically within the 0.01–3.0 V range at a current density of 0.80 mA cm⁻². The Li/Li _x Fe _y O _z (10%) · SiO₂ cell showed a high initial reversible capacity of 1,080 mA h g⁻¹ and a capacity of 600 mA h g⁻¹ at the 30th cycle. Accounting these results is the presence of a SiO₂ phase which stabilizes the structure of the active mass on cycling. The mean charge voltage (1.8 V) and the discharge voltage of 1.0 V versus Li⁺ reference electrode as well as the high reversible capacity indicate that this material is suitable for use as anode in lithium-ion batteries.     

One-pot synthesis of highly luminescent CdTe quantum dots by microwave irradiation reduction and their Hg2+-sensitive properties

A facile one-pot microwave irradiation reduction route has been developed for the synthesis of highly luminescent CdTe quantum dots using Na₂TeO₃ as the Te source in an aqueous environment. The synthesis parameters of this simple and rapid approach, including the reaction temperature and time, the pH of the reaction solution and the molar ratio of the 3-mercaptopropionic acid (MPA) stabilizer to Cd²⁺, have considerable influence on the particle size and photoluminescence quantum yield of the CdTe quantum dots. The photoluminescence quantum yield of CdTe quantum dots prepared using relatively short reaction times (10–40 min) reached 40%–60% (emission peaks at 550–640 nm). Furthermore, the resulting products could be used as fluorescent probes to detect Hg²⁺ ions in aqueous media. The response was linearly proportional to the concentration of Hg²⁺ ion in the range 8.0×10⁻⁹ mol/L to 2.0×10⁻⁶ mol/L with a detection limit of 2.7×10⁻⁹ mol/L. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

Studies on ionic transport properties of a new Ag+ ion conducting composite electrolyte system (1−x)[0·75 AgI: 0·25 AgCl]:xSnO2

A new Ag⁺ ion conducting composite electrolyte system (1−x)[0·75 AgI: 0·25 AgCl]:xSnO₂ using a quenched/annealed [0·75 AgI: 0·25 AgCl] as host compound in place of conventional host AgI, has been investigated. The effects of various preparation methods and soaking time are reported. The composition 0·8[0·75 Agl: 0·25 AgCl]:0·2SnO₂ exhibited optimum conductivity (σ = 8·4 × 10⁻⁴S/cm) with conductivity enhancement of ∼ 10¹ from the annealed host at room temperature. Transport property studies such as electrical conductivity (σ) as a function of temperature using impedance spectroscopy technique, ionic transference number (t _ion) using Wagner’s d.c. polarization method and ionic mobility (μ) by transient ionic current technique were carried out on the optimum conducting composition. The mobile ion concentration (n) was calculated from ‘σ’ and ‘μ’ data.