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1.
In this work, a highly selective membrane triiodide sensor based on a new charge‐transfer complex of bis(2,4‐dimethoxybenzaldehyde)butane‐2,3‐dihydrazone with iodine (Iodide Charge Transfer complex: ICT) as membrane carrier is introduced. The influences of five different solvent mediators on sensitivity and selectivity of the proposed sensor were considered. The best performance was obtained with the membrane composition containing 30% poly (vinyl chloride), 63% DBP, 5% ICT and 2% HTAB. The electrode shows a Nernstian behavior over a very wide triiodide ion concentration range (1.0 × 10?7‐1.0 × 10?2 M), and a detection limit value of 8.0 × 10?8 M. The effect of pH on the potentiometric response of the sensor was also studied, and it was found that the response of the electrode is independent of the pH of the solution in the pH range of 4.0–10. The proposed sensor has a very fast response time (< 12 s), and good selectivities relative to a wide variety of common inorganic and organic anions, including iodide, acetate, bromide, chloride, fluoride, nitrite, nitrate, sulfite, sulfate, cyanide and thiocyanate. In fact the selectivity behavior of the proposed triiodide ion‐selective electrode shows great improvements compared to the previously reported electrodes for triiodide ion. The proposed membrane sensor can be used for at least 6 months without any divergence in the potentials. The electrode was successfully applied as an indicator electrode in the titration of triiodide with thiosulfate ion.  相似文献   

2.
A new triiodide ion‐selective electrode based on a charge‐transfer complex of iodine with ditertbutyl‐dicyclohexyl‐18‐crown‐6 (t‐Bu)2DC18C6 as membrane carrier was prepared. The electrode has a linear dynamic range from 6.3 × 10?3‐5 × 10?6 with a Nernstian response of 58.6 ± 1 mV decade?1 and a detection limit of 1.3 × 10?6 M. The response time of the sensor was 25 s. The membrane could be used for two months without any divergence in potentials. The electrode exhibits an anti‐Hofmeistetr selectivity sequence with a preference for triiodide at pH 2.0‐10.0. The response mechanism of the electrode was investigated by Uv‐Vis spectroscopic technique. The electrode can be used for the determination of ascorbic acid in orange juice.  相似文献   

3.
《Electroanalysis》2004,16(16):1336-1342
The construction, performance characteristics, and application of polymeric membrane (PME) and coated graphite (CGE) thiocyanate‐selective electrodes are reported. The electrodes were prepared by incorporating the complex [Cu(L)](NO3)2 (L=4,7‐bis(3‐aminopropyl)‐1‐thia‐4,7‐diazacyclononane) into a plasiticized poly(vinyl chloride) membrane. The influence of membrane composition, pH of test solution, and foreign ions were investigated. The electrodes reveal Nernstian behavior over a wide SCN? ion concentration range (1.0×10?6–1.0×10?1 M for PME and 5.0×10?7–1.0×10?2 M for CGE) and show fast dynamic response times of 15 s and lower. The proposed sensors show high selectivity towards thiocyanate over several common organic and inorganic anions. They were successfully applied to the direct determination of thiocyanate in urine and saliva of smokers and nonsmokers, and as an indicator electrode in titration of Ag+ ions with thiocyanate.  相似文献   

4.
Novel PVC membrane (PME) and coated graphite (CGE) Cu2+‐selective electrodes based on 5,6,7,8,9,10‐hexahydro‐2H‐1,13,4,7,10‐benzodioxatriazacyclopentadecine‐3,11(4H,12H)‐dione are prepared. The electrodes reveal a Nernstian behavior over wide Cu2+ ion concentration ranges (1.0×10?7–1.0×10?1 M for PME and 1.0×10?8–1.0×10?1 M for CGE) with very low limits of detection (7.8×10?8 M for PME and 9.1×10?9 M for CGE). The potentiometric responses are independent of the pH of the test solutions in the pH range 2.7–6.2. The proposed electrodes possess very good selectivities for Cu2+ over a wide variety of the cations including alkali, alkaline earth, transitions and heavy metal ions. The practical utility of the proposed electrodes have been demonstrated by their use in the study of interactions between copper ions and human growth hormone (hGH) in biological systems, potentiometric titration of copper with EDTA and determination of copper content of a sheep blood serum sample and some other real samples.  相似文献   

5.
The novel compound bis(1,4,7,10‐tetraoxa­cyclo­do­decane)­cadmium(II) decaiodide, [Cd(C8H16O4)2]I10, contains the [Cd(12‐crown‐4)2]2+ complex cation, triiodide ions and iodine mol­ecules. Two triiodide ions and two iodine mol­ecules form isolated twisted I102? rings. The geometry of the complex cation is as expected, e.g.d(Cd—O) = 2.366 (4) and 2.394 (4) Å.  相似文献   

6.
《Electroanalysis》2005,17(17):1534-1539
The construction, performance, and applications of a novel ytterbium(III) sensor based on N‐(2‐pyridyl)‐N′‐(2‐methoxyphenyl)‐thiourea (PMT), as an excellent carrier, in plasticized poly(vinyl chloride) PVC matrix, is described. The influences of membrane composition and pH on the potentiometric response of the sensor were investigated. The sensor exhibits a nice Nernstian response for Yb(III) ion over a wide concentration range of 4 decades of concentration (1.0×10?6–1.0×10?2 M), and a detection limit of 5.0×10?7 M. The response time of the electrodes is between 8 and 10 s, depending on the concentration of ytterbium(III) ions. The proposed sensor can be used for about 8 weeks without any considerable divergence in potential. The sensor revealed very good selectivity for Yb(III) in the presence of several metal ions. The best performance was observed for the membrane containing; 30% PVC, 59% o‐nitrophenyloctyl ether (NPOE) as solvent mediator, 7% PMT, and 4% sodium tetraphenyl borate (NaTPB). It was successfully applied as indicator electrodes in the potentiometric titration of Yb(III) with EDTA and for the determination of fluoride ion in two mouth wash formulations. The proposed La(III) sensor was found to work well under laboratory conditions. It was also used as an indicator electrode in titration of a 1.0×10?4 M of Yb(III) with a standard EDTA solution (1.0×10?2 M). It was also used for determination of Yb(III) ion in Xenotime .  相似文献   

7.
β‐Cyclodextrin functionalized graphene/Ag nanocomposite (β‐CD/GN/Ag) was prepared via a one‐step microwave treatment of a mixture of graphene oxide and AgNO3. β‐CD/GN/Ag was employed as an enhanced element for the sensitive determination of 4‐nitrophenol. A wide linear response to 4‐nitrophenol in the concentration ranges of 1.0×10?8–1.0×10?7 mol/L, and 1.0×10?7–1.5×10?3 mol/L was achieved, with a low detection limit of 8.9×10?10 mol/L (S/N=3). The mechanism and the heterogeneous electron transfer kinetics of the 4‐nitrophenol reduction were discussed according to the rotating disk electrode experiments. Furthermore, the sensing platform has been applied to the determination of 4‐nitrophenol in real samples.  相似文献   

8.
《Electroanalysis》2005,17(19):1746-1754
Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on recently synthesized mercury complexes including Hg(Nmpntb)2 and Hg(Npdntb)2 as new carriers for iodide‐selective electrodes by incorporating the membrane ingredients on the surface of graphite electrodes are reported. The effect of various parameters including the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. Both sensors exhibited Nernstian responses toward iodide over a wide concentration range of 7×10?7 to 0.1 M and 1×10?6 to 0.1 M, with slopes of 59.6±0.8 and 58.9±0.9 mV per decade of iodide concentration and detection limit of 3×10?7 M and 7×10?7 for Hg(Npdntb)2 and Hg(Nmpntb)2, respectively, over a wide pH range of 3–11. The sensors have response times of ≤5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrodes show good ability to discriminate iodide over several inorganic and organic anions. The electrodes were successfully applied to direct determination of iodide in synthetic mixture, waste water and drinking water and as indicator electrodes in precipitation titrations.  相似文献   

9.
《Analytical letters》2012,45(4):683-695
Abstract

A highly selective and sensitive triiodide sensor based on a 2‐(((2‐(((E)‐1‐(2‐hydroxy phenyl) methylidine) amino) phenyl) imino) methyl) phenol with iodine (CTC) as membrane carrier was developed. The electrode revealed a Nernstian behavior over a very wide triiodide‐ion concentration range (5.0×10?8–1.0×10?2 M), and relatively low detection limit (3.0×10?8 M). The potentiometric response is independent of the pH of solution in the pH range of 3.0–10.0. The electrodes manifest advantages of low resistance, very fast response (<12 s), and most importantly, good selectivities relative to a wide variety of inorganic and organic anions, including iodide, bromide, chloride, fluoride, sulfite, sulfate, cyanide, thiocyanate, and acetate. In fact, the selectivity behavior of the proposed triiodide ion‐selective electrode shows great improvements compared to the previously reported electrodes for the triiodide ion. The proposed membrane sensor can be used for at least 6 months without any significant divergences in the potential. The electrode was successfully applied as an indicator electrode in the titration of triiodide with thiosulfate ion.  相似文献   

10.
《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   

11.
《Electroanalysis》2006,18(9):888-893
A poly(vinyl chloride)‐based membrane of dimethyl 1‐acetyl‐8‐oxo‐2,8‐dihydro‐1H‐pyra‐zolo[5,1‐a]isoindole‐2,3‐dicarboxylate as a neutral carrier with sodium tetraphenylborate (NaTPB) as an anion excluder and 2‐nitrophenyl octyl ether (NPOE) as plasticizer was prepared and investigated as a Ba(II)‐selective electrode. The electrode exhibits a Nernstian slope of 29.7±0.4 mV per decade over a wide concentration range (1.0×10?6 to 1.0×10?1 M) with a detection limit of 7.6×10?7 M between pH 3.0 and 11.0. The response time of the sensor is about 10 s and it can be used over a period of 2 months without any divergence in potential. The proposed membrane sensor revealed good selectivity for Ba(II) over a wide variety of other metal ions. It was successfully used in direct determination of barium ions in industrial wastewater samples.  相似文献   

12.
2‐[(N‐Benzyl‐N‐methylamino)methyl]‐1,3‐butadiene (BMAMBD), the first asymmetric tertiary amino‐containing diene‐based monomer, was synthesized by sulfone chemistry and a nickel‐catalyzed Grignard coupling reaction in high purity and good yield. The bulk and solution free‐radical polymerizations of this monomer were studied. Traditional bulk free‐radical polymerization kinetics were observed, giving polymers with 〈Mn〉 values of 21 × 103 to 48 × 103 g/mol (where Mn is the number‐average molecular weight) and polydispersity indices near 1.5. In solution polymerization, polymers with higher molecular weights were obtained in cyclohexane than in tetrahydrofuran (THF) because of the higher chain transfer to the solvent. The chain‐transfer constants calculated for cyclohexane and THF were 1.97 × 10?3 and 5.77 × 10?3, respectively. To further tailor polymer properties, we also completed copolymerization studies with styrene. Kinetic studies showed that BMAMBD incorporated into the polymer chain at a faster rate than styrene. With the Mayo–Lewis equation, the monomer reactivity ratios of BMAMBD and styrene at 75 °C were determined to be 2.6 ± 0.3 and 0.28 ± 0.02, respectively. Altering the composition of BMAMBD in the copolymer from 17 to 93% caused the glass‐transition temperature of the resulting copolymer to decrease from 64 to ?7 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3227–3238, 2001  相似文献   

13.
《Electroanalysis》2002,14(24):1691-1698
Three different recently synthesized aza‐thioether crowns containing a 1,10‐phenanthroline sub‐unit (L1–L3) and a corresponding acyclic ligand (L4) were studied to characterize their abilities as silver ion ionophores in PVC‐membrane electrodes. Novel conventional silver‐selective electrodes with internal reference solution (CONISE) and coated graphite‐solid contact electrodes (SCISE) were prepared based on one of the 15‐membered crowns containing two donating S atoms and two phenanthroline‐N atoms (L1). The electrodes reveal a Nernstian behavior over wide Ag+ ion concentration ranges (1.0×10?5?1.0×10?1 M for CONISE and 5.0×10?8?4.0×10?2 M for SCISE) and very low limits of detection (8.0×10?6 M for CONISE and 3.0×10?8 M for SCISE). The potentiometric response is independent from pH of the solution in the pH range 3.0–8.0. The electrodes manifest advantages of low resistance, very fast response and, most importantly, good selectivities relative to a wide variety of other cations. The electrodes can be used for at least 2 months (for CONISE) and 4 months for (SCISE) without any appreciable divergence in potentials. The electrodes were used as an indicator electrode in the potentiometric titration of Ag+ ion and in the determination of silver in photographic emulsions and in radiographic and photographic films.  相似文献   

14.
《Electroanalysis》2003,15(18):1476-1480
Three nickel(II)‐hexaazacyclotetradecane complexes were studied to characterize their abilities as perchlorate ion carrier in PVC membrane electrodes. The electrodes based on these complexes exhibit Nernstian responses for ClO over very wide concentration ranges (1.0×10?1 ?5.0×10?7 M) with detection limits of 2.0×10?7 ?5.0×10?7 M (20–50 ng/mL). The sensors show very good selectivity for ClO ion in comparison with the most common organic and inorganic anions. The responses of the proposed electrodes are independent of pH in the range of 3.5–11.0. The perchlorate selective membranes show fast response time (<10 s) and can be used for 4–12 weeks without any major deviation. The sensors were successfully used to determine the perchlorate ion in water, wastewater and human urine samples.  相似文献   

15.
《Electroanalysis》2006,18(3):299-306
Different ionophoric species, viz.: 18‐crown‐6 (18C6), dibenzo‐18‐crown‐6 (DB18C6) and calix[6]arene (CAX), as electroactive materials, with 2‐nitrophenyloctylether (2‐NPOE), bis(ethylhexyl)sebacate (DOS), dioctyl phthalate (DOP), and didecyl phthalate (DDP) as plasticizing solvent mediators were used to construct Cr3+ selective electrodes in a PVC matrix in the ratio (w/w) PVC: ionophore: plasticizer (60 : 2 : 120). Seven electrodes out of the fabricated 12 electrodes, gave best results in terms of working concentration range (1.0×10?5?1.0×10?1 M) with a close to Nernstian slope of 18.5 and a Nernstian slope of 20.0 mV/decade of activity. The usable pH range of the sensors is 4.0–7.0. The detection limit of the selected electrodes is ≤1.0×10?7 M. The response time of the sensors is 8–35 s, depending on the concentration of Cr3+ used. The selectivity coefficient values indicate that the electrodes are highly selective for Cr3+ over a number of other cations except Pb2+ and Na+ (for some electrodes). The electrodes have successfully been used to determine Cr3+ in certified and real alloys and in effluents of electroplating shops with a precision as relative standard deviation (RSD)<3%, for each of the proposed Cr3+‐ion selective electrodes. The results obtained by the proposed ISEs are in good agreement with the results obtained by direct flame AAS method.  相似文献   

16.
A novel PVC‐based membrane sensor based on 2,6‐(p‐N,N‐dimethylaminophenyl)‐4‐phenylthiopyrylium perchlorate (DAPP) is described. The electrode exhibits a sub‐Nernstian response to 1‐(beta‐hydroxyethyl)‐2‐methyl‐5‐nitroimidazole (metronidazol) over a relatively wide concentration range (1.0 × 10?1 to 1.0 × 10?5 M) with a detection limit of 8.0 × 10?6 M. The best performance was obtained with the membrane containing 30% poly (vinyl chloride), 50% dibutyl phthalate, 7% DAPP and 13% oleic acid. It has a fast response time (< 30 s) and can be used for at least four weeks without any major deviation. The proposed sensor revealed very good selectivity for metronidazole over a wide variety of common cations, anions and amino acids and could be used in the pH range of 6.0–7.5. It was successfully used for direct determination of metronidazole in an oral synthetic antiprotozoal as an antibacterial agent, in metronidazole tablets, and metronidazole injections and metronidazole gels.  相似文献   

17.
The simple PVC‐based membrane containing N,N′,N″,N′′′‐tetrakis(2‐pyridylmethyl)‐1,4,8,11‐tetraazacyclotetradecane (tpmc) as an ionophore and dibutyl phthalate as a plasticizer, directly coated on a glassy carbon electrode was examined as a new sensor for Cu2+ ions. The potential response was linear within the concentration range of 1.0×10?1–1.0×10?6 M with a Nernstian slope of 28.8 mV/decade and detection limit of 7.0×10?7 M. The electrode was used in aqueous solutions over a wide pH range (1.3–6). The sensor exhibited excellent selectivity for Cu2+ ion over a number of cations and was successfully used in its determination in real samples.  相似文献   

18.
The electrochemical behavior of the Li+/Li couple was studied at polycrystalline tungsten, platinum, copper and aluminum electrodes in tri‐1‐butylmethylammonium bis((trifluoromethyl)sulfonyl)imide ionic liquid mixed with a little propylene carbonate at 30 °C. Lithium cations were introduced into the ionic liquid by dissolution of lithium bis((trifluoromethyl)sulfonyl)imide which is highly soluble in ionic liquid. Propylene carbonate was used to reduce the viscosity of this ionic liquid in order to enhance the mass transfer and to additionally improve the stability of lithium deposits. At the tungsten and copper electrodes, the cyclic voltammetric behavior of a Li+/Li couple is a quasi‐reversible reaction. At the platinum electrode, the behavior becomes very complicated because of the alloy formation. Coulombic efficiency was used to evaluate the stability of lithium deposits at each electrode. The aluminum electrode showed the best efficiency due to the formation of Li‐Al alloy. However, lowest efficiency was obtained at the platinum electrode because of the low redox reversibility of the lithium in the Li‐Pt alloy. The diffusion coefficient of lithium cation in this solution was 1.0 ± 0.1 × 10?;7 cm2 s?;1 as determined by chronopotentiometry. The best coulombic efficiency obtained at the Al electrode is 97% but dropped to about 90% after 12 hours. The self‐discharge current of the lithium deposits at the Al electrode was 0.4 μA/cm2 during the experimental period.  相似文献   

19.
A new electrochemical method was proposed for the determination of adenosine‐5′‐triphosphate (ATP) based on the electrooxidation at a molecular wire (MW) modified carbon paste electrode (CPE), which was fabricated with diphenylacetylene (DPA) as the binder. A single well‐defined irreversible oxidation peak of ATP appeared on MW‐CPE with adsorption‐controlled process and enhanced electrochemical response in a pH 3.0 Britton‐Robinson buffer solution, which was due to the presence of high conductive DPA in the electrode. The electrochemical parameters of ATP were calculated with the electron transfer coefficient (α) as 0.54, the electron transfer number (n) as 1.9, the apparent heterogeneous electron transfer rate constant (ks) as 2.67 × 10?5 s?1 and the surface coverage (ΓT) as 4.15 × 10?10 mol cm?2. Under the selected conditions the oxidation peak current was proportional to ATP concentration in the range from 1.0 × 10?7 mol L?1 to 2.0 × 10?3 mol L?1 with the detection limit as 1.28 × 10?8 mol L?1 (3σ) by sensitive differential pulse voltammetry. The proposed method showed good selectivity without the interferences of coexisting substances and was successful applied to the ATP injection samples detection.  相似文献   

20.
Anion‐selective solvent polymeric membrane based on hydrogen bond‐forming, neutral ionophores with amide or acyl‐hydrazine groups are described. The use of the two calix[4]arenes results in anion‐selective electrodes with a selectivity for phosphate. The electrodes of the optimum characteristic have the composition of 1 wt% ionophore, 66 wt% o‐NPOE, 33 wt% poly (vinyl chloride) (PVC) and TDMACl (15 or 30 mol% relative to the ionophore 1 and 2 , respectively). The optimized membrane electrodes show Nernstian responses towards monohydrogen phosphate (?29.1 and ?29.3 mV/decade) based on ionophore 1 and 2 , respectively, in a wide concentration range (1.0×10?5 to 1.0×10?2 or 1.0×10?5 to 1.0×10?1 M). The selectivity coefficients are determined with the fixed interference method and the activity ratio method. The electrodes display an anti‐Hofmeister series selectivity pattern and highly selective for HPO42? over Cl?, Br?, CH3COO?, NO3? and SO42?. The lifetime of the electrodes is at least 1 month and their response time is found to be 25 s. The proposed sensors could be put to analytical use both by direct potentiometry as well as potentiometric titration.  相似文献   

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