Autoprotolysis constants and standardization of the glass electrode in acetonitrile-water mixtures. Effect of solvent composition

Standard e.m.f.s for the cell GE/HCl/AgCl/Ag/Pt (GE=glass electrode) in acetonitrile-water mixtures containing 0–70% (w/w) of acetonitrile were obtained. Values of the autoprotolysis constant, K_ap, of these mixed solvents were also determined from e.m.f. measurements of the cell GE/KCl + KS/AgCl/Ag/Pt. The influence of variations in the solvent composition on pK_ap values was evaluated. Over the whole of the composition range studied the pK_ap values were linearly correlated with the mole fraction of acetonitrile and with the reciprocal of the relative permittivity of solvent mixtures. Linear relationships were also obtained for pK_ap values vs. the Kamlet-Taft π^★ polarizability/dipolarity parameter in the range 0–50% (w/w).     

Holographic sensors for the determination of ionic strength

Holographic sensors for monitoring ionic strength have been fabricated from charged sulphonate and quaternary ammonium monomers, incorporated into thin, polymeric hydrogel films which were transformed into volume holograms. The diffraction wavelength or reflected colour of the holograms was used to characterise their swelling or de-swelling behaviour as a function of ionic strength in various media. The effects of co-monomer structure, buffer composition, ion composition, pH and temperature were evaluated, whilst the reversibility and reproducibility of the sensor was also assessed. An acrylamide-based hologram containing equal molar amounts of negatively and positively charged monomers was shown to be able to quantify ionic strength independent of the identity of the ionic species present in the test solution. The sensor was fully reversible, free of hysteresis and exhibited little response to pH between 3 and 9 and temperature within the range 20-45 °C. The system was successfully used to quantify the ionic strength of milk solutions, which contain a complex mixture of ions and biological components.     

Solution ionic strength effect on gold nanoparticle solution color transition

Unmodified and modified gold nanoparticles are proposed as sensors using the red to blue transition as an indicator. This work indicates that ionic content is an important variable to track in analytical samples and during the sensor fabrication processes. Mono and multivalent salts where the titrants for a standard gold nanoparticle solution. Multivalent cation salt titrants exhibited a greater sensitivity to color change than monovalent cation salts. The data suggest that specific surface adsorption is the predominant mechanism for the red to blue color change not aggregation. The 3-7 nm Debye length for divalent cations versus the 0.5-1.5 nm for monovalent cations indicates surface electrodynamic resonance effects are an important factor in the observed color changes.     

An ionic liquid-type carbon paste electrode for electrochemical investigation and determination of calcium dobesilate

An ionic liquid-type carbon paste electrode (IL-CPE) had been fabricated by replacing non-conductive organic binders with a conductive room temperature ionic liquid, 1-pentyl-3-methylimidazolium hexafluorophosphate (PMIMPF₆). The electrochemical responses of calcium dobesilate were investigated at the IL-CPE and the traditional carbon paste electrode (T-CPE) in 0.05 mol L⁻¹ H₂SO₄, respectively. The results showed the superiority of IL-CPE to T-CPE in terms of provision of higher sensitivity, faster electron transfer and better reversibility. A novel method for determination of calcium dobesilate was proposed. The oxidation peak current was rectilinear with calcium dobesilate concentration in the range of 8.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹, with a detection limit of 4.0 × 10⁻⁷ mol L⁻¹(S/N = 3) by differential pulse voltammetry. The proposed method was applied to directly determine calcium dobesilate in capsule and urine samples.     

Effect of ionic strength and protein concentration on the transport of proteins through chitosan/polystyrene sulfonate multilayer membrane

The influence of ionic strength and protein concentration on the transport of bovine serum albumin (BSA), ovalbumin and lysozyme through chitosan (CHI)/polystyrenesulfonate (PSS) multilayers on polyether sulfone supports are investigated under ultrafiltration conditions. The percentage transmission and flux of BSA, ovalbumin and lysozyme were found to increase with increase in salt concentration in the protein. The percentage transmission of BSA through 9 bilayer membrane was found to increase from 5.3 to 115.6 when the salt concentration was varied from 0 to 1 M. It was observed that 0.1 M NaCl in BSA solution is capable of permeating all the BSA. When the salt concentration in BSA was further increased, a negative solute rejection (solute enrichment in permeate) was found to take place. With 9 bilayer membrane, the percentage transmission of ovalbumin was found to increase from 23.3 to 125.8 when the salt concentration in protein was increased from 0 to 0.05 M. The effect of protein concentration on protein transport is studied taking BSA as a model protein. BSA was rejected by the multilayer membrane at all the studied concentrations (0.25, 0.5, 1 and 2 mg/ml). With increase in feed concentration, maximum rejection of protein occurred at higher number of CHI/PSS bilayers. BSA solution flux was found to decrease with an increase in BSA concentration. This study indicates that it is possible to fine tune the transport properties of proteins through multilayer membranes by varying the concentration and ionic strength of protein solutions.     

Effect of equilibrium potential on anodic peaks of a reversible electrode process in conditions of stripping voltammetry at a linear alteration of potential on a thin-film mercury electrode

The full contour of a stripping-voltammetry peak for a reversible electrode process in conditions of boundedly semi-infinite and symmetrical diffusion on a thin-film mercury electrode at a linearly altering potential is calculated with an exact explicit equation allowing for the equilibrium-potential effect in a broad range of values of parameter H (which are defined by the film thickness, potential scan rate, and diffusion coefficient). The height, position of maximum, and full width at half-maximum of anodic peaks are evaluated as a function of parameter H and equilibrium potential. The latter is shown to exert substantial influence on the parameters and shape of anodic peaks.To the Centennial of B.N. KabanovDeceasedTranslated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 69–75.Original Russian Text Copyright © 2005 by Nazarov, Stromberg, Larionova.     

Sensitive voltammetric determination of rutin at an ionic liquid modified carbon paste electrode

An ionic liquid modified carbon paste electrode (IL/CPE) had been fabricated by using hydrophilic ionic liquid 1-amyl-3-methylimidazolium bromide ([AMIM]Br) as a modifier. The IL/CPE was characterized by scanning electron microscope and voltammetry. Electrochemical behavior of rutin at the IL/CPE had been investigated in pH 3.29 Britton-Robinson (B-R) buffer solution by cyclic voltammetry (CV) and square wave voltammetry (SWV). The experimental results suggested that the modified electrode exhibited an electrocatalytic activity toward the redox of rutin. The electron transfer coefficient (α) and the standard rate constant (k_s) of rutin at the modified electrode were calculated. Under the selected conditions, the reduction peak current was linearly dependent on the concentration of rutin in the range of 4.0 × 10⁻⁸ to 1.0 × 10⁻⁵ mol L⁻¹ (r = 0.9998), with a detection limit of 1.0 × 10⁻⁸ mol L⁻¹ (S/N = 3). The relative standard deviation (R.S.D.) for six times successful determination of 8.0 × 10⁻⁷ mol L⁻¹ rutin was 1.2%. The proposed method was applied to determine rutin in tablet and urine sample. In addition, the IL/CPE exhibited a distinct advantage of simple preparation, surface renewal, good reproducibility and good stability.     

Kinetic studies for sorption of amino acids using a strong anion-exchange resin. Effect of ionic strength

This work deals with the influence of the ionic strength on the sorption of L-phenylalanine and L-tyrosine by a strong basic anion-exchange resin, converted to the hydroxide form with sodium hydroxide. Equilibrium uptake isotherms were obtained for phenylalanine and tyrosine by carrying out batch experiments at different ionic strength values of the solution. The model used to correlate these results is the modified Langmuir equation which has been applied with success to biological systems. Batch kinetic experiments were performed using a packed bed of differential length inserted in a liquid circulation loop and in which the ionic strength of the solution was varied. Moreover, an experiment at variable pH for tyrosine was also performed. Experimental transient concentration profiles were compared to those predicted by the pore diffusion model and enabled the estimation of the intraparticle diffusivities for phenylalanine and tyrosine.     

Development and characterization of ion selective electrode for the assay of antimony

The construction and general performance characteristics of two novel potentiometric carbon paste electrodes (CPE) responsive to antimony are described. These sensors are based on the use of the ion associate complexes of tetraiodoantimonate (TIA) anion with cetylpyridinium (CP) and triphenyl tetrazolium (TPT) counter cations as ion exchange site in a carbon paste matrix. The two sensors exhibits fast, stable and near-Nernstian for the mono charged TIA anion over the concentration range 1 × 10⁻³ to 10⁻⁶ M at 25 °C in the pH range 4-10 with anionic slope of 58.0 ± 0.5 and 55.0 ± 0.7 per concentration decade for TIA-CP and TIA-TPT, respectively. The lower detection limits are 4 and 5 × 10⁻⁶ M and response time are 20 and 30 s in the same order of both electrodes. Selectivity coefficients for antimony relative to a number of different cations and anions were investigated. There is negligible interference from many inorganic cation and anion except for Hg²⁺, Cd²⁺, and Bi³⁺; however, their effect were eliminated by EDTA. The determination of 1.0-120.0 μg/ml of antimony in aqueous solutions shows an average recovery of 99.0 and 97.5% with relative standard deviation of 2.0% for both electrodes at 40 μg/ml. The determination of antimony in wastewater and some antibilharzial compounds using the proposed electrodes gave results that compare favorably with those obtained by the atomic absorption spectrometric method. Precipitation titrations involving cetylpyridinium chloride as titrant are monitored with both electrodes with inflection point of 180 and 100 mV for TIA-CP and TIA-TPT, respectively.     

On the asymmetry of thermodynamic fluctuations of the electrode potential

The asymmetry of thermodynamic fluctuations of the equilibrium electrode potential and the asymmetry of thermodynamic fluctuations of the electrical double layer charge is characterized quantitatively on the basis of third-order noise spectra.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 131–136.Original Russian Text Copyright © 2005 by Grafov.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

The electrochemical properties of a platinum electrode in functionalized room temperature imidazolium ionic liquids

The electrochemical behavior of a platinum electrode in a set of 1-alkyl ether (and 1-alkyl)-3-methylimidazolium room-temperature ionic liquids (RTILs) 1–3 ([C_xO_yMim]⁺[Anion]⁻ or [C_xMim]⁺[Anion]⁻, where Mim = 3-methylimidazolium; C_xO_y = 1-alkyl ether; C₇O₃ = -(CH₂)₂O(CH₂)₂O(CH₂)₂OCH₃; C₃O₁ = -(CH₂)₂OCH₃; C_x = 1-alkyl; C₁₀ = C₁₀H₂₁; C₄ = C₄H₉; and ) was studied by cyclic voltammetry and electrical conductivity. This complementary set of imidazolium RTILs allowed us to explore the effect of the imidazolium cation and the counter-ion, both of which affected the electrochemical window of these RTILs. Various electrochemical events with low current values were observed, which diminished the electrochemical windows. Interestingly, RTILs 2b [1-(2-methoxyethyl)-3-methylimidazolium tetrafluoroborate] and 2d [1-butyl-3-methylimidazolium tetrafluoroborate] showed quasireversible charge transfer processes. The length of the functional group attached to the imidazolium cation was shown to be of great influence as larger electrochemical windows, as well as lower electrical conductivities, were obtained with the longer C₇O₃ and C₁₀ functional groups. The largest electrochemical window of 2.0 V was achieved with RTIL 2c, 1-decyl-3-methylimidazolium tetrafluoroborate. Dedicated to the memory of Prof. Francisco Nart.     

Electrochemical behavior and differential pulse voltammetric determination of paracetamol at a carbon ionic liquid electrode

The electrochemical behavior of paracetamol in 0.1 M acetate buffer solution (pH 4.6) was investigated at a traditional carbon paste electrode (TCPE) and a carbon ionic liquid electrode (CILE) fabricated by replacing nonconductive organic binders with a conductive hydrophobic room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF₆). The results showed that the CILE exhibited better reversibility for the electrochemical redox of paracetamol. The oxidation potential of paracetamol at the CILE is +0.462 V, which is approximately 232 mV lower than that at the TCPE; the oxidation peak current response is nine times higher than that at the TCPE. The differential pulse voltammetric determination of paracetamol at the CILE was established based on this behavior. After optimizing several important parameters controlling the performance of paracetamol at the CILE, the oxidation peak current versus paracetamol concentration at the CILE showed linearity in the range from 1.0 μM to 2.0 mM (R ²  = 0.9992) with a detection limit of 0.3 μM (S/N = 3). The method has been applied to the determination of paracetamol in tablets and urine samples and the average recovery of paracetamol was 98.5% and 99.3%, respectively. The proposed CILE showed good sensitivity and reproducible response without influence of interferents commonly existing in pharmaceutical and urine samples. Figure CV curves of paracetamol illustrate the enhanced electrochemical behavior of paracetamol at the CILE (b), which forms the basis for the differential pulse voltammetric determination of paracetamol     

The effect of sonication on glass electrodes

This communication describes observations made on the disturbing effect of ultrasound on the functioning of glass electrodes. It was observed that the signal of glass electrodes drops significantly, with as much as several pH units, if sonication is applied to the sample solution. The effect was studied for a variety of electrolyte solutions and for several glass electrode makes, and was always found to be reversible and reproducible. The quality and the concentration of the electrolyte, as well as the ultrasonic power applied were seen to strongly influence the magnitude of the effect. These findings suggests that (i) if a glass electrode is being used to follow chemical reactions in sonicated solutions, irradiation should be intermitted for the time of measurements, and (ii) the phenomenon may provide an alternative method for sensing ultrasound or mapping ultrasound energy distribution.     

Application of ionic liquid modified carbon ceramic electrode for the sensitive voltammetric detection of rutin

An ionic liquid (IL) modified carbon ceramic electrode (CCE) was designed and further used for the voltammetric detection of rutin in this paper. IL-CCE was prepared by mixing graphite powder with 1-butyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) doped silicate sol-gel matrix together and further characterized by different methods. Then electrochemical behaviors of rutin on the IL-CCE were investigated by different electrochemical methods such as cyclic voltammetry and differential pulse voltammetry (DPV). Due to the presence of IL in the CCE, an enhanced electrochemical response of rutin appeared with a pair of well-defined redox peaks in pH 2.5 phosphate buffer solution (PBS). The electrochemical behaviors of rutin on the IL-CCE were carefully investigated. Under the selected conditions the oxidation peak currents exhibited good linear relationship with the rutin concentration in the range from 0.3 to 100.0 μmol/L with the detection limit as 0.09 μmol/L (3σ). The proposed method was further applied to the rutin tablets sample detection with satisfactory results.     

Impact of surface immobilization and solution ionic strength on the formal potential of immobilized cytochrome C

Four different self-assembled monolayer (SAM) electrode systems were examined electrochemically in order to better understand surface charge effects on the redox thermodynamics of immobilized horse heart cytochrome c (cyt c). Neutralization of protein surface charge upon adsorption on anionic COOH-terminated SAMs was found to cause substantial changes in the formal potential, as determined by cyclic voltammetry. For cyt c immobilized on negatively charged surfaces, the formal potential shifted to more negative values as the ionic strength was decreased, which is opposite to the trend displayed by solution cyt c. In contrast, immobilization to uncharged interfaces resulted in an ionic strength dependence for cyt c that is similar to its solution behavior. The results provide insight into the importance of surface charge on the formal potential of cyt c.     

Highly sensitive determination of promazine in pharmaceutical and biological samples using a ZnO nanoparticle-modified ionic liquid carbon paste electrode

In this work we describe the first report for the determination of promazine using a nanostructuremodified ionic liquid carbon paste electrode in aqueous solutions. To achieve this goal, a novel modified carbon paste electrode using ZnO nanoparticles and 1-methyl-3-butylimidazolium bromide as a binder(ZnO/NPs/ILs/CPE) was fabricated. The oxidation peak potential of promazine at the surface of the ZnO/NPs/ILs/CPE appeared at 685 m V, which was about 65 m V lower than the oxidation potential at the surface of CPE under similar conditions. Also, the peak current was increased to about 4.0 times higher at the surface of ZnO/NPs/ILs/CPE compared to that of CPE. The linear response range and detection limit were found to be 0.08–450 and 0.04 mmol/L, respectively. The modified electrode was successfully used for the determination of promazine in real samples with satisfactory results.     

Potentiometric detection of citrate in beverages using a graphite carbon electrode

The development, evaluation and application of a simple and low-cost graphite carbon electrode for the direct determination of citrate in food samples are described here. The electrode exhibits a linear response with a slope of −29.0 ± 1.0 mV decade⁻¹ in a concentration range of 0.07-7.0 mmol L⁻¹ in 0.1 mol L⁻¹ KCl/1.0 mmol L⁻¹ phosphate buffer solution with a limit of detection of 3.0 μmol L⁻¹. The electrode is easily constructed at a relatively low cost and has a fast time response (within 120 s) with no significant changes in its performance characteristics. The performance of the graphite sensor was tested to determine citrate in beverage samples (juices and an isotonic drink), and the results were validated against a reference procedure. The proposed method is quick, inexpensive, selective and sensitive, and is based entirely on conventional instrumentation.     

膜流动电位测试中Ag-AgCl电极的制备及稳定性研究

膜的动电特性研究中,往往采用流动电位方法。该方法中,Ag-Ag Cl测试电极的质量是影响测试准确性的关键要素。本文采用正交试验设计和方差分析,着重考察电解法制备Ag-Ag Cl电极过程中,电流强度(I)、氯化时间(t)、电解质溶液浓度(CHCl)、电极来源(n)、烘烤温度(T)、活化电极溶液浓度(CKCl)等因素对Ag-Ag Cl电极稳定性的影响。得到Ag-Ag Cl电极的最优制备参数为:电流密度3.0m A/cm2,氯化时间50min,盐酸浓度0.1mol·L-1,烘烤温度120℃,活化电极溶液(KCl)浓度0.001mol·L-1;最显著影响因素为电极来源,显著影响因素为氯化时间和烘烤温度。对最优条件组合下制备的AgAg Cl电极,进行了稳定性实验,结果表明:制备的电极具有较好的稳定性,24h内电极电位漂移量小于0.10mv,7天内电极电位漂移量小于0.2mv;在聚偏氟乙烯中空纤维超滤膜流动电位测试中,流动电位与流动压差具有良好的线性和可重复性,回归曲线R20.99,变化规律符合Helmholtz-Smoluehowski公式,可以较好满足膜的流动电位测试要求。     

Acid-base equilibria of phthalic acid in saline media: ion association from Pitzer equations

The protonation constants of 1,2-benzenedicarboxylic acid (phthalic acid) at 25 °C in NaCl and CaCl₂ (ionic strengths ranging from 0.1 to 2 mol kg⁻¹) were determined potentiometrically, and the results were analyzed by means of Pitzer equations. The values of the logarithm of the first and second dissociation constants ranged from 2.730 and 4.948 (in 0.101 mol kg⁻¹ NaCl) to 2.449 and 3.984 (in 0.624 mol kg⁻¹ CaCl₂), respectively. Tabulated interaction parameters for the inorganic species involved along with salting coefficients estimated from literature allowed the calculation of new interaction parameters for the phthalate-Na⁺/Ca²⁺ systems. The specific ion interaction model considered seems to account for the influence of the formation of weak complexes of phthalate with calcium ions on the equilibrium constants.