Mercury(II) selective membrane electrode based on 1,3-bis(2-methoxybenzene)triazene

A plasticized poly (vinyl chloride) membrane electrode based on 1,3-bis(2-methoxybenzene)triazene (MBT) for highly selective determination of mercury(II) has been developed. The electrode showed a good Nernstian response (30.2 ± 0.3 mV decade^− 1) over a wide concentration range (1.0 × 10^− 7−1.0 × 10^− 2 mol L^− 1). The limit of detection was 5.0 × 10^− 8 mol L^− 1. The electrode has a response time about 15 s and can be used for at least 1 month without observing any deviation from Nernstain response. The proposed electrode revealed an excellent selectivity toward mercury(II) ion over a wide variety of alkali, alkaline earth, transition, and heavy metal ions and could be used in the pH range 2.6–4.2. The electrode was used in the determination of Hg²⁺ in aqueous samples and as an indicator electrode in potentiometric titration of Hg(II) ions.     

Adsorption of dyes on Sahara desert sand

Sahara desert sand (SaDeS) was employed as a mineral sorbent for retaining organic dyes from aqueous solutions. Natural sand has demonstrated a strong affinity for organic dyes but significantly lost its adsorption capacity when it was washed with water. Therefore, characterization of both natural and water washed sand was performed by XRD, BET, SEM and FTIR techniques. It was found that water-soluble kyanite, which is detected in natural sand, is the dominant factor affecting adsorbance of cationic dyes. The sand adsorbs over 75% of cationic dyes but less than 21% for anionic ones. Among the dyes studied, Methylene Blue (MB) demonstrated the strongest affinity for Sahara desert sand (Q_e = 11.98 mg/g, for initial dye solution concentration 3.5 × 10⁻⁵ mol/L). The effects of initial dye concentration, the amount of the adsorbent, the temperature and the pH of the solution on adsorption capacity were tested by using Methylene Blue as model dye. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were applied. It was concluded that adsorption of Methylene Blue on Sahara desert sand followed pseudo-second order kinetics. Gibbs free energy, enthalpy change and entropy change were calculated and found −6411 J/mol, −30360 J/mol and −76.58 J/mol K, respectively. These values indicate that the adsorption is an exothermic process and has a spontaneous nature at low temperatures.     

Electrochemical behaviour of Cu24Zn5Al alloy in alkaline medium in the presence of chloride ions and benzotriazole

This paper deals with electrochemical behaviour of Cu24Zn5Al alloy in a sodium tetraborate solution (borax), in the presence of chloride ions and benzotriazole. It was found that during anodic polarization of the investigated alloy, in a sodium tetraborate solution, at lower potentials, copper (I)-oxide formed on the alloy surface. The voltammograms show peak potential shifts corresponding to the formation of Cu₂O towards more positive values with longer immersion time. It was found that chloride ions had an activating effect in a sodium tetraborate solution containing various concentrations of chloride ions (0.001, 0.005, 0.010, 0.050 and 0.100 mol dm⁻³ Cl⁻). It was observed that Cu24Zn5Al alloy corroded more intensely in more concentrated solutions and with longer exposure to Cl⁻. Investigations of the effect of inhibitor concentrations (8.4 × 10⁻⁶, 8.4 × 10⁻⁵, 8.4 × 10⁻⁴ and 8.4 × 10⁻³ mol dm⁻³ BTA in 0.1 mol dm⁻³ borax solution) showed that BTA had a good protective effect. The inhibiting effect of BTA was also confirmed with various times of immersion of this alloy in a 1.7 × 10⁻² mol dm⁻³ solution of this inhibitor.     

The bromination kinetics of phenolic compounds in aqueous solution

The purpose of this study was to investigate the bromination kinetics of selected phenolic compounds in aqueous solutions over the pH range of 5–11. The experiment results indicated that the reaction of hypobromous acid with the phenoxide ions controlled the overall reaction rate, whereas the reaction between hypobromite ion and the phenoxide ions and the reaction between hypobromous acid and the undissociated phenolic species were considered to be negligible respectively in the pH range of 7–9. The apparent second-order rate constants of the reaction of hypobromous acid with the phenoxide ions ranged from 7.9 × 10⁶ M⁻¹ s⁻¹ for 3-chlorophenol to 6.5 × 10⁸ M⁻¹ s⁻¹ for 3-methoxyphenol, respectively. The Hammett correlation could be successfully used to estimate the reactivity of bromine with substituted phenols and the linear regression was log(k₂) = −2.85б + 8.00. The rate constants of the reaction of bromine with phenol-like organic compounds were about three orders of magnitude higher than with chlorine and two to three orders of magnitude lower than with ozone.     

Biosorptive uptake of methylene blue using Mediterranean green alga Enteromorpha spp.

Batch biosorption experiments were carried out for the removal of methylene blue, a basic dye, from aqueous solution using raw and dried Enteromorpha spp., Mediterranean green alga. A series of assays were undertaken to assess the effect of the system variables, i.e. contact time, solution pH and sorbent amount. The results had showed that sorption capacity was optimal using 6–10 solution pH range (i.e. maximum adsorption capacity of 274 mg/g). The minimum sorbent concentration experimentally found to be sufficient to reach the total removal of the dye molecules from the aqueous solution was 5 g/L. Besides, equilibrium data were fitted using five linearisable isotherm models. The related results showed that the experimental data were very well represented by the Langmuir model for the linear regression analysis and both the Langmuir and Redlich–Peterson isotherm models for the non-linear analysis. In both cases, such modelling behaviour confirms the monolayer coverage of methylene blue molecules onto energetically homogenous Enteromopha surface. In addition, an exhaustive comparative study was done to situate this marine biomass among other proposed sorbents.     

Toxicity of mercury on in vitro development of parthenogenetic eggs of a freshwater cladoceran Daphnia carinata

A series of recently synthesized benzo- and pyridine-substituted macrocyclic diamides were studied to characterize their abilities as lead ion carriers in PVC membrane electrodes. The electrode based on 3,15,21-triaza-4,5;13,14-dibenzo-6,9,12-trioxabicycloheneicosa-1,17,19-triene-2,16-dione exhibits a Nernstian response for Pb²⁺ ions over a wide concentration range (1.3 × 10⁻² to 3.6 × 10⁻⁶ mol L⁻¹) with a limit of detection of 2.0 × 10⁻⁶ mol L⁻¹ (0.4 ppm). The response time of the sensor is 16 s, and the membrane can be used for more than two months without observing any deviation. The electrode revealed comparatively good selectivities with respect to many cations including alkali earth, transition and heavy metal ions. The proposed sensor could be used in pH range of 3.7–6.5. It was used as an indicator electrode in potentiometric titration of chromate ions with a lead ion solution.     

Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: Equilibrium, kinetic and thermodynamic study

A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1 h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g⁻¹. Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R² > 0.99). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0–40 °C.     

Application of statistical design of experiment with desirability function for the removal of organophosphorus pesticide from aqueous solution by low-cost material

This paper deals with the multiple response optimization for the removal of organophosphorus pesticide quinalphos [QP: O,O-diethyl O-2-quinoxalinyl phosphorothioate] from the aqueous solution onto low-cost material and tried to overcome the drawbacks of univariate optimization. Used tea leaves were used as low-cost adsorbent and batch equilibration method was followed for this study. A Box–Behnken design was used to develop response model and desirability function was then used for simultaneous optimization of all affecting parameters in order to achieve the highest removal% of quinalphos. The optimum conditions of factors predicted for quinalphos removal% were found to be: pH 8.83, concentration 7 mg L⁻¹ and dose 0.40 g. Under these conditions, maximum removal% of quinalphos was obtained 96.31%. Considering the above optimum conditions, the adsorption isotherms were developed and provided adsorption capacity of 196.07 μg g⁻¹ by using Langmuir equation, indicating that used tea leaves may be applied as a low-cost material for pesticides removal from aqueous matrices.     

Clarified sludge (basic oxygen furnace sludge) – an adsorbent for removal of Pb(II) from aqueous solutions – kinetics, thermodynamics and desorption studies

The basic oxygen furnace waste generated in steel plant has been used as a low cost adsorbent for the removal of Pb(II) from aqueous solution. The effect of pH, adsorbent dosage, initial metal ion concentration, contact time and temperature on adsorption process was studied in batch experiments. Results of the equilibrium experiments showed that the solution pH was the key factor affecting the adsorption characteristics. Optimum pH for the adsorption was found to be 5 with corresponding adsorbent dosage level of 5 g/L. The equilibrium was achieved within 1 h of contact time. Kinetics data were best described by pseudo second order model. The effective particle diffusion coefficient of Pb(II) is the order of 10⁻¹⁰ m²/s. The maximum uptake was 92.5 mg/g. The adsorption data can be well fitted by Freundlich isotherm. The result of the equilibrium studies showed that the solution pH was the key factor affecting the adsorption. External mass transfer analysis was also carried out for the adsorption process. The thermodynamic studies indicated that the adsorption is spontaneous and endothermic. The sorption energy (10.1745 kJ/mol) calculated from Dubinin–Radushkevich isotherm indicated that the adsorption process is chemical in nature. Desorption studies were carried out using dilute mineral acids to elucidate the mechanism of adsorption. Application studies were carried out considering the economic viewpoint of wastewater treatment plant operations.     

Electrical and optical properties of 12CaO·7Al2O3 electride doped indium tin oxide thin film deposited by RF magnetron co-sputtering

12CaO·7Al₂O₃ electride (C12A7:e⁻) doped indium tin oxide (ITO) (ITO:C12A7:e⁻) thin films were fabricated on a glass substrate by an RF magnetron co-sputtering system with increasing number of C12A7:e⁻ chips (from 1 to 7) and at various oxygen partial pressure ratios. The optical transmittance of the ITO:C12A7:e⁻ thin film was higher than 70% in the visible wavelength region. In the electrical properties of the thin film, a decrease of the carrier concentration from 2.6 × 10²⁰ cm^− 3 to 2.1 × 10¹⁸ cm^− 3 and increase of the resistivity from 1.4 × 10^− 3 Ω cm to 4.1 × 10^− 1 Ω cm were observed with increasing number of C12A7:e⁻ chips and oxygen partial pressure ratios. It was also observed that the Hall mobility was decreased from 17.27 cm²·V^− 1·s^− 1 to 5.13 cm²·V^− 1·s^− 1. The work function of the ITO thin film was reduced by doping it with C12A7:e⁻.     

Electrochemical determination of cadmium(II) at platinum electrode modified with kaolin by square wave voltammetry

In this work, determination of cadmium(II) using square wave voltammetry (SWV) was described. The method is based on accumulation of these metal ions on kaolin platinum electrode (K/Pt). The K/Pt performance was optimized with respect to the surface modification and operating conditions. The optimized conditions were obtained in pH of 5.0 and accumulation time of 25 min. Under the optimal conditions, the relationship between the peak current versus concentration was linear over the range of 9 × 10⁻⁸ to 8.3 × 10⁻⁶ mol L⁻¹. The detection limit (DL, 3σ) was 5.4 × 10⁻⁹ mol L⁻¹. The analytical methodology was successfully applied to monitor the Cd(II) content in natural water. Interferences were also evaluated.     

Sorption behavior of nano-TiO2 for the removal of selenium ions from aqueous solution

Titanium dioxide nanoparticles were employed for the sorption of selenium ions from aqueous solution. The process was studied in detail by varying the sorption time, pH, and temperature. The sorption was found to be fast, and to reach equilibrium basically within 5.0 min. The sorption has been optimized with respect to the pH, maximum sorption has been achieved from solution of pH 2–6. Sorbed Se(IV) and Se(VI) were desorbed with 2.0 mL 0.1 mol L⁻¹ NaOH. The kinetics and thermodynamics of the sorption of Se(IV) onto Nano-TiO₂ have been studied. The kinetic experimental data properly correlate with the second-order kinetic model (k₂ = 0.69 g mg⁻¹ min⁻¹, 293 K). The overall rate process appears to be influenced by both boundary layer diffusion and intraparticle diffusion. The sorption data could be well interpreted by the Langmuir sorption isotherm. The mean energy of adsorption (14.46 kJ mol⁻¹) was calculated from the Dubinin–Radushkevich (D–R) adsorption isotherm at room temperature. The thermodynamic parameters for the sorption were also determined, and the ΔH⁰ and ΔG⁰ values indicate exothermic behavior.     

Growth, thermal and spectroscopic characteristics of LiNd(WO4)2 crystal

Crystal growth, thermal and optical characteristics of LiNd(WO₄)₂ crystal have been investigated. The LiNd(WO₄)₂ crystal up to Ø15 × 32 mm³ has been grown by Czochralski technique. The hardness is about 5.0 Mohs’ scale. The specific heat at 50 °C is 0.42 J g⁻¹ K⁻¹. The thermal expansion coefficient for c- and a- axes is 1.107 × 10⁻⁵ and 2.104 × 10⁻⁵ K⁻¹, respectively. The absorption and fluorescence spectra and the fluorescence decay curve of LiNd(WO₄)₂ crystal were measured at room temperature. Some spectroscopic parameters such as the intensity parameters, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and emission cross sections were estimated.     

Voltammetric determination of ethamsylate in bulk solution and pharmaceutical tablet by nano-material composite-film coated electrode

A sensitive electrochemical method was described for voltammetric determination of ethamsylate at a glassy carbon electrode (GCE) coated with a nano-material thin film. In this work, a nanometer material, namely, multi-wall carbon nanotubes (MWCNT) was dispersed successfully into water in the presence of dihexadecyl hydrogen phosphate (DHP) and a MWCNT–DHP composite film was conveniently obtained on the GCE surface. The electrochemical behavior of ethamsylate at this modified electrode was investigated and a pair of reversible redox peak was observed. Compared with the electrochemical response of ethamsylate at the bare GCE, the separation of peak potential (ΔE_p) of ethamsylate decreased obviously from 438 to 40 mV and the current density of redox peaks increased greatly. Based on this, differential pulse voltammetry (DPV) was employed to determine ethamsylate. Various experimental parameters such as pH value of the supporting electrolyte, the amount of modifier and so on were optimized. Under optimal conditions, a linear response of ethamsylate was obtained in the range from 1.0 × 10^− 6 to 2.0 × 10^− 5 mol/L, and the detection limit was 6.0 × 10^− 7 mol/L. The proposed method was successfully applied to detect ethamsylate in pharmaceutical samples.     

Removal of Methylene Blue by Activated Carbon Prepared from Waste in a Fixed-Bed Column

In this study, the ability of activated carbon prepared from waste to adsorb methylene blue from aqueous solution was investigated in a fixed-bed column. The effect of flow rate and inlet methylene blue concentration on the adsorption characteristics of activated carbon was investigated at 25°C. Freundlich and Langmuir adsorption models have been used to represent the column equilibrium data. The Langmuir constants of Q_o and b were determined as 6.38 mg · g^?1 and 0.34 L · mg^?1, respectively. The results showed that the equilibrium data fitted Langmuir isotherm within the concentration range studied. Four kinetic models, Adams-Bohart, Wolborska, Thomas, and Yoon-Nelson, were applied to experimental data to predict the break-through curves and determine the characteristic parameters of the column useful for process design. Results also indicate that the adsorption process can only deal with lower flow rates and lower concentrations of methylene blue solution if a high percentage of removal is required for extended periods. All models were found suitable for methylene blue adsorption onto activated carbon.     

Biosensor enhanced by glucose oxidase biomimetic membrane containing the platinum and silica nanoparticles

In this paper, glucose biosensor is fabricated with immobilization of glucose oxidase (GOx) in platinum and silica sol. The glucose biosensor combined with Pt and SiO₂ nanoparticles could make full use of the properties of nanoparticles. A set of experimental results indicates that the current response for the enzyme electrode containing platinum and silica nanoparticles increases from 0.32 µA cm^− 2 to 33 µA cm^− 2 in the solution of 10 mM β-D-glucose. The linear range is 3 × 10^− 5 to 3.8 × 10^− 3 M with a detection limit of 2 × 10^− 5 M at 3σ. The effects of the various volume ratios of Pt and SiO₂ sols with respect to the current response and the stability of the enzyme electrodes are studied.     

Determination of cadmium at ultra-trace levels by CPE–molecular fluorescence combined methodology

A highly sensitive micelle-mediated extraction methodology for the preconcentration and determination of trace levels of cadmium by molecular fluorescence has been developed. Metal was complexed with o-phenanthroline (o-phen) and eosin (eo) at pH 7.6 in buffer Tris medium and quantitatively extracted into a small volume of surfactant-rich phase of PONPE 7.5 after centrifugating. The chemical variables affecting cloud point extraction (CPE) were evaluated and optimized. The RSD for six replicates of cadmium determinations at 0.84 μg L⁻¹ level was 1.17%. The linearity range using the preconcentration system was between 2.79 × 10⁻³ μg L⁻¹ and 2.81 μg L⁻¹ with a correlation coefficient of 0.99. Under the optimal conditions, it obtained a LOD of 8.38 × 10⁻⁴ μg L⁻¹ and LOQ of 2.79 × 10⁻³ μg L⁻¹. The method presented good sensitivity and selectivity and was applied to the determination of trace amounts of cadmium in commercially bottled mineral water, tap water and water well samples with satisfactory results. The proposed method is an innovative application of CPE-luminescence to metal analysis comparable in sensitivity and accuracy with atomic spectroscopies.     

Novel oxidative electrophilic coupling reactions of phenoxazine derivatives with MBTH and their applications to spectrophotometric determination of residual chlorine in drinking water and environmental water samples

Novel, sensitive and rapid spectrophotometric methods, using phenoxazine (PNZ), 2-chlorophe-noxazine (CPN) and 2-trifluoromethylphenoxazine (TPN) as chromogenic reagents for the determination of residual chlorine are proposed. The methods are based on the reduction of chlorine by an electrophilic coupling reagent, 3-methyl-2-benzothiazoline hydrazono hydrochloride hydrate (MBTH) in mild hydrochloric acid medium and subsequent coupling with PNZ, CPN or TPN. The blue color formed in the reaction showed maximum absorbance at 680–690 nm and obeyed Beer's law over the range 0.1–2.2 μg ml⁻¹. The molar absorptivity values with PNZ, CPN and TPN were 2.80 × 10⁴, 2.67 × 10⁴ and 1.91 × 10⁴ l mol⁻¹ cm⁻¹ and Sandell's sensitivity values were 0.028, 0.027 and 0.028 μg cm⁻² respectively. The proposed methods were successfully applied in the determination of residual chlorine in drinking water and environmental water samples. The performance of proposed methods was evaluated in terms of Student's t-test and variance ratio F-test which indicated the significance of proposed methods over the standard spectrophotometric method.     

Cyclic plasticity of single crystal nickel oriented for single slip

The cyclic deformation behavior of single crystal nickel was investigated by performing uniaxial fully reversed constant plastic strain amplitude fatigue experiments at plastic shear strain amplitudes ranging from 1.1 × 10⁻⁴ to 8.8 × 10⁻³. Digitally acquired stress–strain hysteresis loops were used to calculate friction and back stresses and to relate the shapes of the loops to the evolving dislocation structures and magnetomechanical effects. The results indicate that the cyclic stress–strain curve exhibits a plateau of 50 MPa between plastic strain amplitudes of 1 × 10⁻⁴ and 7 × 10⁻³. Saturation friction stress, calculated using the Cottrell method, is reasonably constant over the entire range of plastic strain amplitudes at a value of 15 MPa. The back stress is 35 MPa within the plateau and increases to 48 MPa at the highest strain amplitude. When cycled at low plastic strain amplitude, magnetomechanical effects account for a significant portion of the measured inelastic strain.     

Growth and optical characterizations of (Ba0.32Sr0.68)5Nb4O15 crystal

(Ba_0.32Sr_0.68)₅Nb₄O₁₅ crystal with sizes of Ø 17 × 35 mm was grown successfully by Czochralski technique method. The thermal anisotropy was discussed. The principal coefficients of thermal expansion along (100), (010), (001) directions were precisely measured to be 1.308 × 10^− 5, 1.288 × 10^− 5, 1.478 × 10^− 5 K^− 1, respectively. Its optical transparency range has been measured and found to span from 323 to 5500 nm. The bands present in the IR spectra were identified and assigned to the corresponding vibration modes of NbO₆ anions.