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1.
The electrode characteristics and selectivities of PVC-based thiocyanate selective polymeric membrane electrode (PME) incorporating the newly synthesized zinc complex of 6,7:14,15-Bzo2-10,11-(4-methylbenzene)-[15]-6,8,12,14-tetraene-9,12-N2-1,5-O2 (I 1 ) and zinc complex of 6,7:14,15-Bzo2-10,11-(4-methylbenzene)-[15]-6,14-diene-9,12-dimethylacrylate-9,12-N2-1,5-O2 (I 2 ) are reported here. The best response was observed with the membrane having a composition of I2:PVC:o-NPOE:HTAB in the ratio of 6:33:59:2 (w/w; milligram). This electrode exhibited Nernstian slope for thiocyanate ions over working concentration range of 4.4 × 10−7 to 1.0 × 10−2 mol L−1 with detection limit of 2.2 × 10−7 mol L−1. The performance of this electrode was compared with coated graphite electrode (CGE), which showed better response characteristics w.r.t Nernstian slope 59.0 ± 0.2 mV decade−1 activity, wide concentration range of 8.9 × 10−8 to 1.0 × 10−2 mol L−1 and detection limit of 6.7 × 10−8 mol L−1. The response time for CGE and PME was found to be 8 and 10 s, respectively. The proposed electrode (CGE) was successfully applied to direct determination of thiocyanate in biological and environmental samples and also as indicator electrode in potentiometric titration of SCN ion.  相似文献   

2.
《Electroanalysis》2005,17(9):776-782
Three recently synthesized Schiff's bases were studied to characterize their ability as Cr3+ ion carrier in PVC‐membrane electrodes. The polymeric membrane (PME) and coated glassy carbon (CGCE) electrodes based on 2‐hydroxybenzaldehyde‐O,O′‐(1,2‐dioxetane‐1,2‐diyl) oxime (L1) exhibited Nernstian responses for Cr3+ ion over wide concentration ranges (1.5×10?6–8.0×10?3 M for PME and 4.0×10?7–3.0×10?3 M for CGCE) and very low limits of detection (1.0×10?6 M for PME and 2.0×10?7 M for CGCE). The proposed potentiometric sensors manifest advantages of relatively fast response and, most importantly, good selectivities relative to a wide variety of other cations. The selectivity behavior of the proposed Cr3+ ion‐selective electrodes revealed a considerable improvement compared to the best previously PVC‐membrane electrodes for chromium(III) ion. The potentiometric responses of the electrodes are independent of pH of the test solution in the pH range 3.0–6.0. The electrodes were successfully applied to determine chromium(III) in water samples.  相似文献   

3.
A method was developed for determining selenium with a self-made ion-selective electrode was developed. This electrode was made by using Ag2Se as electroactive material. Optimal working conditions and interferences were investigated. The electrode exhibits good potentiometric response for Se2− ions over the concentration range from 6 × 10−7 mol · L−1 to 1 × 10−4 mol · L−1 with a Nernstian slope of 28 ± 1 mV per decade and a detection limit of about 4.5 × 10−7 mol · L−1. It was used over six months and exhibits good selectivity and sensitivity towards Se2−. The method was applied to determine selenium in biological materials. The recovery ranges between 92% and 105.5%, and the relative standard derivation is less than 3.6% (n = 6).  相似文献   

4.
 A differential pulse voltammetric method for the determination of nitrate has been described, which is applicable to the analysis of natural water samples with nitrate levels greater than 2.8 × 10−6 M. A reduction peak for the nitrate ions at a freshly copper plated glassy carbon electrode was observed at about −0.50 V vs Ag ∣AgCl∣KClsatd electrode in a solution of 2.0 × 10−2 M Cu2+, 0.5 M H2SO4 and 1.0 × 10−3 M KCl and exploited for analytical purposes. The working linear range was established by regression analysis and found to extend from 2.8 ×10−6 M to 8.0 × 10−5 M. The proposed method was applied for the determination of nitrate in natural waters. The detection limit of the method was 2.8 × 10−6 M and the sensitivity was 0.9683 A·L/mol. The possible interferences by some ions such as phosphate, nitrite and some halides were determined and found to lead to shifts of the peak position and increasing the peak heights. Received March 15, 1999. Revision July 9, 1999.  相似文献   

5.
The electrochemical behaviors of metol on an ionic liquid N-butylpyridinium hexafluorophosphate modified carbon paste electrode (IL-CPE) were studied in this paper. The results indicated that a pair of well-defined quasi-reversible redox peaks of metol appeared with the decrease of overpotential and the increase of redox peak current, which was the characteristics of electrocatalytic oxidation. The electrocatalytic mechanism was discussed and the electrochemical parameters were calculated with results of the charge-transfer coefficient (α) as 0.45, the electrode reaction rate constant (k s) as 4.02 × 10−3 s−1, and the diffusion coefficient (D) as 6.35 × 10−5 cm2/s. Under the optimal conditions, the anodic peak current was linear with the metol concentration in the range of 5.0 × 10−6 ∼ 1.0 × 10−3 mol/L (n = 11, γ = 0.994) and the detection limit was estimated as 2.33 × 10−6 mol/L (3σ). The proposed method was successfully applied to determination of metol content in synthetic samples and photographic solutions.  相似文献   

6.
 A PVC membrane electrode selective for cetyldimethylethylammonium (CDEA) ion was prepared. The active element is a plasticized poly vinyl chloride membrane containing a dissolved ion associate complex of CDEA with phosphotungstic acid (PTA). The electrode showed a near-Nernstian response within the CDEA+ concentration range 2.34 × 10−6 to 1.96 × 10−4 M at 25 ± 1^C, good selectivity, and is usable within the pH range 3.5–9.0. The isothermal temperature coefficient of the electrode amounted to −0.00012 V/°C. The electrode has been used for the direct determination of cetyldimethylethylammonium bromide either by the standard addition method or by potentiometric titration against PTA. Received January 1, 1998. Revision June 13, 2000.  相似文献   

7.
《Electroanalysis》2004,16(4):282-288
Five recently synthesized macrocyclic diamides were investigated to characterize their ability as beryllium ion carriers in potentiometric PVC‐membrane electrodes. The electrodes based on 1,15‐diaza‐3,4;12,13‐dibenzo‐5,8,11‐trioxabicyclo[13,2,2] heptadecane‐2,14‐dione exhibited a Nernstian response for Be2+ ion over wide concentration ranges (from 3.0×10?6 to 3.0×10?2 M for polymeric membrane electrode, PME, and from 5.0×10?7 to 2.0×10?2 M for coated glassy carbon electrode, CGCE) and very low detection limits (2.0 ×10?6 M for PME and 4.0×10?7 M for (CGCE). The electrodes possess low resistances, fast responses, satisfactory reproducibilities and, most importantly, good selectivities relative to a variety of other common cations. The potentiometric response of the electrodes is independent of pH of test solution in the pH range of 4.0–7.5. The proposed sensors were used to determine beryllium ion in water samples.  相似文献   

8.
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  相似文献   

9.
Liquid polymer membrane electrodes based on nickel and manganese phthalocyanines were examined for use as anion-selective electrodes. The electrodes were prepared by incorporating the ionophores into plasticized poly(vinyl chloride) membranes, which were directly coated onto the surfaces of graphite electrodes. The resulting electrodes demonstrate near-Nernstian responses over a wide linear range of perchlorate anion (5 × 10−7 to 1 × 10−1 M). The electrodes have a fast response time, submicromolar detection limits (5 × 10−7 M perchlorate), and could be used over a wide pH range of 3.5–10. The influences of lipophilic cationic and anionic additives on the response properties of the electrodes were investigated. The proposed sensors revealed high selectivity for perchlorate over a number of common inorganic and organic anions. The highest selectivity was observed for the electrode based on manganese phthalocyanine in the presence of the lipophilic anionic additive sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. Application of the electrodes to determine perchlorate in tap water and human urine is also reported.   相似文献   

10.
 The construction and electrochemical response characteristics of poly(vinyl) chloride matrix membrane sensors for menadione (vitamin K3) are described. Membranes incorporating the ion association complexes of menadione anion with bathophenanthroline nickel(II) and iron(II) as electroactive materials show linear response for menadione over the range 10−1–10−5M with anionic slopes of 58.2–51.4 mV per concentration decade. Both sensors exhibit fast response time (20–30 s), low detection limit (2 × 10−5M), good stability (4–6 weeks) and selectivity coefficient (10−1–10−3). Direct potentiometric determination of menadione under static and hydrodynamic mode of operations shows average accuracies of 98.8 and 98.5% with relative standard deviations of 0.6% and 1.3%, respectively. Application of the method for the determination of menadione in human plasma gives favourable results compared with those obtained by the standard spectrophotometric method. Received February 26, 2001. Revision October 1, 2001.  相似文献   

11.
A potentiometric azide-selective sensor based on the use of iron(III) hydrotris(3,5-dimethylpyrazolyl)borate acetylacetonate chloride [TpMe2Fe(acac)Cl] as a neutral carrier for an azide-selective electrode is reported. Effect of various plasticizers, viz. o-nitrophenyloctyl ether (o-NPOE), dioctylphthalate (DOP), dibutylphthalate (DBP), and benzylacetate (BA), and an anion excluder, hexadecyltrimethylammonium bromide (HTAB), with [TpMe2Fe(acac)Cl] complex in poly(vinyl chloride) (PVC) were studied. The best performance was obtained with a membrane composition of [TpMe2Fe(acac)Cl]/HTAB/DOP/PVC in a ratio of 5:2:190:100 (w/w). The sensor exhibits significantly enhanced selectivity toward azide ions over the concentration range 6.3 × 10−7 to 1.0 × 10−2 M with a lower detection limit of 3.8 × 10–7 M and a Nernstian slope of 59.4 ± 1.1 mV decade−1. Influences of the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrode. Fast and stable response, good reproducibility, long-term stability and applicability over a wide pH range (3.5–9.0) are demonstrated. The sensor has a response time of 14 s and can be used for at least 45 days without any considerable divergence in the potential response. The proposed electrode shows fairly good discrimination of azide from several inorganic and organic anions. It was successfully applied to the direct determination of azide in orange juice, tea extracts and human urine samples.  相似文献   

12.
Two new PVC membrane electrodes that are highly selective to Ag(I) ions were prepared using (L1) calyx[4]arene (L2) as two suitable neutral carriers. The silver(I) ion selective electrodes exhibit a good response for silver ion over a wide concentration range of 1.0 × 10−1 to 4.2 × 10−6 M (L1) and 1.0 × 10−1 to 6.5 × 10−6 M (L2) with a Nernstian slope of 60 mV per decade (L1) and 58 mV per decade (L2) at 25°C, and was found to be very selective, precise, and usable within the pH range 4.0–8.0. They have a response time of <15 s and can be used for at least 3 months without any measurable divergence in potential. The proposed sensors show a fairly good discriminating ability towards Ag+ ion in comparison to some hard and soft metal ions. The electrodes were used as indicator electrodes in the potentiometric titration of silver ion and in the determination of Ag+ in photographic emulsion and radiographic and photographic films. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 7, pp. 862–868. The article is published in the original.  相似文献   

13.
Newly developed, simple, low-cost and sensitive ion-selective electrodes have been proposed for determination of some antiepileptic drugs such as lamotrigine, felbamate, and primidone in their pharmaceutical preparations as well as in biological fluids. The electrodes are based on poly(vinyl chloride) membranes doped with drug–tetraphenyl borate (TPB) or drug–phosphotungstic acid (PT) ion-pair complexes as molecular recognition materials. The novel electrodes displayed rapid Nernstian responses with detection limits of approximately 10−7 M. Calibration graphs were linear over the ranges 5.2 × 10−7–1.0 × 10−3, 1.5 × 10−6–1.0 × 10−3, and 2.6 × 10−7–1.0 × 10−3 M for drug–TPB and 5.8 × 10−7–1.0 × 10−3, 1.8 × 10−7–1.0 × 10−3, and 6.6 × 10−7–1.0 × 10−3 M for drug–PT electrodes, respectively, with slopes ranging from 52.3 to 62.3 mV/decade. The membranes developed have potential stability for up to 1 month and proved to be highly selective for the drugs investigated over other ions and excipients. The results show that the selectivity of the ion-selective electrodes is influenced significantly by the plasticizer. The proposed electrodes were successfully applied in the determination of these drugs in pharmaceutical preparations in four batches of different expiry dates. Statistical Student’s t test and F test showed insignificant systematic error between the ion-selective electrode methods developed and a standard method. Comparison of the results obtained using the proposed electrodes with those found using a reference method showed that the ion-selective electrode technique is sensitive, reliable, and can be used with very good accuracy and high percentage recovery without pretreatment procedures of the samples to minimize interfering matrix effects. Figure Structure of lamotrigine, felbanate and primidone  相似文献   

14.
The electrocatalytic activity of a Prussian blue (PB) film on the aluminum electrode by taking advantage of the metallic palladium characteristic as an electron-transfer bridge (PB/Pd–Al) for electrooxidation of 2-methyl-3-hydroxy-4,5-bis (hydroxyl–methyl) pyridine (pyridoxine) is described. The catalytic activity of PB was explored in terms of FeIII [FeIII (CN)6]/FeIII [FeII (CN)6]1− system. The best mediated oxidation of pyridoxine (PN) on the PB/Pd–Al-modified electrode was achieved in 0.5 M KNO3 + 0.2 M potassium acetate of pH 6 at scan rate of 20 mV s−1. The mechanism and kinetics of the catalytic oxidation reaction of PN were monitored by cyclic voltammetry and chronoamperometry. The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. The charge transfer-rate limiting reaction step is found to be a one-electron abstraction, whereas a two-electron charge transfer reaction is the overall oxidation reaction of PN by forming pyridoxal. The value of α, k, and D are 0.5, 1.2 × 102 M−1 s−1, and 1.4 × 10−5 cm2 s−1, respectively. Further examination of the modified electrodes shows that the modifying layers (PB) on the Pd–Al substrate have reproducible behavior and a high level of stability after posing it in the electrolyte or Pyridoxine solutions for a long time.  相似文献   

15.
The electrochemical behaviour of polycrystalline silver electrodes in Na2CO3 solutions was studied under potentiodynamic and potentiostatic conditions and complemented with X-ray diffraction analysis. Potentiodynamic E/i anodic curves exhibit active passive transition prior to an oxygen evolution reaction. The active region involves a small peak AI followed by a major peak AII before the passive region. Peak AI is assigned to the formation of an Ag2O layer while peak AII is due to the formation of an Ag2CO3 layer. The height of the anodic peaks increases with increasing Na2CO3 concentration, scan rate and temperature. The effect of increasing additions of NaClO4 on the electrochemical behaviour of Ag in Na2CO3 solutions was investigated. The perchlorate ions stimulate the active dissolution of Ag, presumably as a result of the formation of soluble AgClO4 salt. In the passive region, ClO 4 ions tend to break down the dual passive film, leading to pitting corrosion at a certain critical pitting potential. The pitting potential decreases with ClO 4 concentration. Potentiostatic current/time transients showed that the formation of Ag2O and Ag2CO3 layers involves a nucleation and growth mechanism under diffusion control. However, in the presence of ClO 4 ions, the incubation time for pit initiation decreases on increasing the anodic potential step. Received: 3 July 1998 / Accepted: 10 March 1999  相似文献   

16.
 The construction of a plasticised PVC matrix-type promazinium cation-selective membrane electrode and its use in the potentiometric determination of promazine hydrochloride in pharmaceutical preparations are described. It is based on the use of the ion-associate species, formed by promazinium cation and tetraphenylborate (TPB) counter ion. The basic electrode performance characteristics are evaluated according to IUPAC recommendations. It exhibited a linear response for 1 × 10−2−1 × 10−5 M of promazine hydrochloride solutions with a cationic Nernstian slope over the pH range 2–6. Common organic and inorganic cations showed negligible interference. Direct potentiometric determination of 1 × 10−2−1 × 10−5 M aqueous promazine hydrochloride using this membrane electrode system showed an average recovery of 99.5% with a mean standard deviation of 1.5%. This electrode was successfully used for monitoring the titration of promazine hydrochloride with sodium tetraphenyl borate and for determining promazine hydrochloride in ampoules. Received June 15, 2001 Revision November 6, 2001  相似文献   

17.
Molecular wires containing copper(II) (CuMW), in the form of the coordination polymer (Cu(II)4(bpp)4(maa)8(H2O)2).2H2O (bpp=1,3-bis(4-pyridyl)propane, maa=2-methylacrylic acid), and multiwalled carbon nanotubes (CNT) have been combined to prepare a paste electrode (CuMW/CNT/PE). The voltammetric response of the CuMW/CNT/PE to metformin (MET) was significantly greater than that of electrodes prepared from other materials, because of both the surface effect of CuMW and CNT and coordination of MET with the Cu(II) ion in the CuMW. A novel voltammetric method for determination of MET is proposed. In pH 7.2 Britton–Robinson buffer, using single sweep voltammetry, the second-order derivative peak current for oxidation of MET at 0.97 V (relative to SCE) increased linearly with MET concentration in the range 9.0 × 10−7–5.0 × 10−5 mol L−1 and the detection limit was 6.5 × 10−7 mol L−1. Figure When a combination of molecular wires containing copper(II) (CuMW) and multiwalled carbon nanotubes (CNT) was used to prepare a paste electrode (CuMW/CNT/PE) the voltammetric response to metformin (curve c) was significantly higher than that at a carbon/PE (curve a) or a CNT/PE (curve b), because of the amplification effect of CNT and CuMW. A novel voltammetric method is proposed for determination of MET  相似文献   

18.
SiO2/ZrO2/C carbon ceramic material with composition (in wt%) SiO2 = 50, ZrO2 = 20, and C = 30 was prepared by the sol–gel-processing method. A high-resolution transmission electron microscopy image showed that ZrO2 and the graphite particles are well dispersed inside the matrix. The electrical conductivity obtained for the pressed disks of the material was 18 S cm−1, indicating that C particles are also well interconnected inside the solid. An electrode modified with flavin adenine dinucleotide (FAD) prepared by immersing the solid SiO2/ZrO2/C, molded as a pressed disk, inside a FAD solution (1.0 × 10−3 mol L−1) was used to investigate the electrocatalytic reduction of bromate and iodate. The reduction of both ions occurred at a peak potential of −0.41 V vs. the saturated calomel reference electrode. The linear response range (lrr) and detection limit (dl) were: BrO3 , lrr = 4.98 × 10−5–1.23 × 10−3 mol L−1 and dl = 2.33 μmol L−1; IO3 , lrr = 4.98 × 10−5 up to 2.42 × 10−3 and dl = 1.46 μmol L−1 for iodate.  相似文献   

19.
The results of kinetic and equilibrium experiments with the set of reaction of proton abstraction from 4-nitrophenyl[bis(ethylsulphonyl)]methane in acetonitrile are reported. Two strong organic bases are used: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD). The rates of proton transfer reaction have been measured by T-jump method in the presence of perchlorate of the appropriate base as a common cation BH+ and supporting electrolyte-tetrabutylammonium perchlorate (TBAP) in the temperature range between 20–40°C are: k H =1.32×107−2.00×107 and 2.82×107−4.84×107 dm 3mol−1s−1 for MTBD and TBD respectively. The enthalpies of activation ΔH MTBD =13.5 and ΔH TBD =18.1 kJmol−1. The entropies of activation are negative: ΔS MTBD =−62.3 and ΔS TBD =−40.3 Jmol−1K−1. The change of the absorbance of the anion of 4-nitrophenyl[bis9ethylsulphonyl)]methane at the temperature 25°C in the presence of common cation BH+ gives the equilibrium constants K=705 and 906 M−1 for MTBD and TBD respectively. Kinetic and equilibrium results are discussed. The possible mechanism of proton transfer reaction between 4-nitrophenyl[bis(ethylsulphonyl)]methane and cyclic organic bases: MTBD and TBD in acetonitrile is proposed.  相似文献   

20.
The plasticized polymer electrolytes composed of poly(epichlorohydrin-ethyleneoxide) (P(ECH-EO)) as host polymer, lithium perchlorate (LiClO4) as salt, γ-butyrolactone (γ-BL), and propylene carbonate (PC) as plasticizer have been prepared by simple solution casting technique. The effect of mixture of plasticizers γ-BL and PC on conductivity of the polymer electrolyte P(ECH-EO):LiClO4 has been studied. The band at 457 cm−1 in the Raman spectra of plasticized polymer electrolyte is attributed to both the ring twisting mode of PC and the perchlorate ν 2(ClO4) bending. The maximum conductivity value is observed to be 4.5 × 10−4 S cm−1 at 303 K for 60P(ECH-EO):15PC:10γ-BL:15LiClO4 electrolyte system. In the present investigation, an attempt has been made to correlate the Raman and conductivity data.  相似文献   

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