Past, present, and future of applications of electroanalytical techniques in analytical and physical organic chemistry

After a brief introduction describing the main milestones in the development of DC polarography (DCP) as well as linear sweep (LSV) and cyclic voltammetry (CV), attention is paid to first applications of DCP in the reduction of organic compounds. In aqueous solutions the electron transfer (ET) is often accompanied by a proton transfer. Limiting currents in DCP enable investigation of kinetics of chemical reactions preceding ET. Dependence of the limiting current on concentration of a reagent, like H⁺ or OH^{??/sup> ions, enables determination of rate constants (k) of very fast reactions, with k values between 104 and 1010?L?mol???s??, comparable with those studied by relaxation methods. Application of CV is most advantageous for investigation of rates of chemical reactions following the ET. Comparison of analytical applications of DCP (reductions) with those of LSV (oxidations) is given. Apart from fast reactions taking place before the ET in the solution in the vicinity of the electrode surface, DCP can also be used for investigation of slower reactions, taking place in the bulk of the solution. Data obtained by DCP for determination of equilibrium (K) and rate (k) constants of reactions of organic compounds. Hence, DCP can be used in physical organic chemistry of solutions, in some cases complementing data obtained by UV–vis spectrophotometry. Some examples of determinations of K and k are given. Uncertain future of practical analytical applications of DCP and LSV is discussed as is the brighter future of applications in physical organic chemistry. As the main factor limiting successful applications is considered the limited opportunity for education of future research advisors in academia and group supervisors in industry.}     

Zinc-Selective Membrane Electrode Based On 5, 6, 14, 15-Dibenzo-l, 4-Dioxa-8, 12-Diazacyclopentadecane-5, 14-Diene

ABSTRACT

A new PVC membrane for zinc ions based on DBDA15C4 as membrane carrier was prepared. The electrode shows a linear stable response over a wide concentration range (5.0 × 10^?5-1.0 × 10^?1 M) with a slope of 22 mV/decade and a limit of detection of 3.0 × 10^?5 M (2.0 μg/ml). It has a very short response time of less than 5 s and can be use for at least 11 months without any divergence in potential. The zinc ion-selective electrode exhibited very good selectivities with respect to alkali, alkaline earth and some transition and heavy metal ions and could be used in a pH range 1.5-7.0. It was successfully applied for the direct determination of zinc in a pharmaceutical sample and, as an indicator electrode, in potentiometric titration of Zn²⁺ ions.     

Atomic absorption spectrometric and potentiometric microdetermination of the nitro and nitroso groups in organic compounds

New simple, rapid, accurate, and selective methods are described for microdetermination of the nitro and nitroso groups in organic compounds. These are based on reduction with cadmium metal and 0.05 M HCl whereby 6 and 4 equivalents of the cadmium ions are released per nitro and nitroso groups, respectively. The cadmium ions are measured by atomic absorption spectrometry at 228.8 nm, potentiometrically by titration with EDTA using the cadmium ion selective electrode, and visually by EDTA titration using Eriochrome Black T indicator. Results with an average recovery of 98% and a mean standard deviation of 1.3% are obtainable and no interferences are caused by many nitrogen, oxygen, and sulfur functional groups.     

Simultaneous microdetermination of iodine and sulfur in organic compounds

A simple and rapid method for the simultaneous microdetermination of iodine and sulfur in organic compounds is described. The procedure utilizes the Schöniger flask method for the combustion, the iodide ions titration with 0.01 N mercuric perchlorate solution and diphenylcarbazone as indicator and the sulfate ions titration with 0.01 M barium perchlorate solution and dimethylsulfonazo III as indicator. The results obtained are in good agreement with calculated values.     

Preparation and characterization of a new organic-inorganic nano-composite poly-o-toluidine Th(IV) phosphate: Its analytical applications as cation-exchanger and in making ion-selective electrode

An organic-inorganic hybrid poly-o-toluidine Th(IV) phosphate was chemically synthesized by mixing ortho-tolidine into the gel of Th(IV) phosphate in different mixing volume ratios, concentration of inorganic reactant with a fixed mixing volume ratios of organic polymer. The physico-chemical characterization was carried out by elemental analysis, TEM, SEM, XRD, FTIR and simultaneous TGA-DTA studies. The ion-exchange capacity, chemical stability, effect of eluant concentration, elution behavior and pH titration studies were also carried out to understand the ion-exchange capabilities. The distribution studies revealed that the cation-exchange material is highly selective for Hg²⁺, which is an important environmental pollutant. Due to selective nature of the cation-exchanger ion-selective membrane electrode was fabricated for the determination of Hg(II) ions in solutions. The analytical utility of this electrode was established by employing it as an indicator electrode in electrometric titrations.     

Lower limits of the potentiometric microtitration of chloride with silver ions

The lower levels of the potentiometric titration of chloride with silver ions were investigated. The titrant was 0.001 N acetonic silver perchlorate. The titration media were acetone and acetic anhydride:acetone (4:1). A silver sulfide ion-selective indicator electrode and a double-junction reference electrode were use to monitor emf's. This titration is limited only by the trace amounts of chloride in the reagents used. Satisfactory results and well-defined titration curves were obtained down to 7 μg of chloride per 50 ml of solution (0.2 μmol; 4 × 10^?6N).A small polarization current can be used to enhance the potentiometric breaks of this titration. In an 80% methanolic medium with 0.001 N aqueous silver nitrate and a polarization current of ?0.4 μA, the lower practical limit of this titration was near 22.3 μg of chloride (1.26 × 10^?5N).     

A mercury(II) ion-selective electrode based on neutral salicylaldehyde thiosemicarbazone

A new ion-selective PVC membrane electrode based on salicylaldehyde thiosemicarbazone as an ionophore is developed successfully as sensor for mercury(II) ions. The electrode shows excellent potentiometric response characteristics and displays a linear log[Hg²⁺] versus EMF response over a wide concentration range of 1.778×10⁻⁶-1.0×10⁻¹ M with Nernstian slope of 29 mV per decade with the detection limit of 1.0×10⁻⁶ M. The response time of the electrode is less than 30 s and the membrane electrode operates well in the pH range of 1.0-3.0. The lifetime of the sensor is about 2 months. The electrode shows better selectivity towards Hg²⁺ ions in comparison with the alkali, alkaline and some heavy metal ions; most of these metal ions do not show significant interference (K^Pot_Hg,M values of the order of 10⁻³-10⁻⁴). The present sensor showed comparable or even better performance vis-à-vis similar PVC based ion-selective electrodes reported in literature. The sensor was also applied as an indicator electrode for potentiometric titration of Hg²⁺ions with I⁻ and Cr₂O₇²⁻.     

Lead(II)-Selective Membrane Electrode Based on Tetraphenylporphyrin

ABSTRACT

A PVC membrane electrode for Pb² ions based on tetraphenylporphyrin was prepared. The sensor exhibits a Nernstian response for lead ions over a wide concentration range (1.0 x 10^?5-1.0 x 10^?2 M). The limit of detection is 8.5 x 10^?6M. It has a response time of 15 s and can be used for at least three months without any divergence in potential. The proposed electrode shows a fairly good discriminating ability towards Pb² ion in comparison to some alkali, alkaline earth, transition and heavy metal ions. The electrode can be used in the pH range 5.0 to 7.5. It was used as an indicator electrode in potentiometric titration of lead ion.     

Highly Selective PVC‐Based Membrane Electrode Based on 2,6‐Diphenylpyrylium Fluoroborate

A highly selective PVC‐membrane electrode based on 2,6‐diphenylpyrylium fluoroborate is presented. The electrode reveals a Nernstian potentiometric response for sulfate ion over a wide concentration range (5.0 × 10^?6‐1.0 × 10^?1 M). The electrode has a response time of about 10 s and can be used for at least 2 months without any divergence. The proposed sensor revealed very good selectivities for sulfate over a wide variety of common organic and inorganic anions and could be used over a wide pH range (2.5–9.5). The detection limit of the sensor is 3.0 × 10^?6 M. It was successfully applied to the direct determination of salbutamol, paramomycin tablets, and as an indicator electrode for potentiometric titration of sulfate ions with barium ions.     

A novel ion selective membrane potentiometric sensor for direct determination of Fe(III) in the presence of Fe(II)

A new PVC membrane potentiometric sensor that is highly selective to Fe(III) ions was prepared by using 2-[(2-hydroxy-1-propenyl-buta-1,3-dienylimino)-methyl]-4-p-tolylazo-phenol [HPDTP] as a suitable carrier. The electrode exhibits a linear response for iron(III) ions over a wide concentration range (3.5 × 10⁻⁶ to 4.0 × 10⁻²) with a super Nernstian slope of 28.5 (±0.5) per decade. The electrode can be used in the pH range from 4.5 to 6.5. The proposed sensor shows fairly a good discriminating ability towards Fe³⁺ ion in comparison to some hard and soft metals such as Fe²⁺, Cd²⁺, Cu²⁺, Al³⁺ and Ca²⁺. It has a response time of <15 s and can be used for at least 2 months without any measurable divergence in response characteristics. The electrode was used in the direct determination of Fe³⁺ in aqueous samples and as an indicator electrode in potentiometric titration of Fe(III) ions.     

Novel coated-graphite membrane sensor based on N,N′-dimethylcyanodiaza-18-crown-6 for the determination of ultra-trace amounts of lead

A novel selective membrane electrode for determination of ultra-trace amount of lead was prepared. The PVC membrane containing N,N′-dimethylcyanodiaza-18-cown-6 (DMCDA18C6) directly coated on a graphite electrode, exhibits a Nernstian response for Pb²⁺ ions over a very wide concentration range (from 1.0×10⁻² to 1.0×10⁻⁷ M) with a limit of detection of 7.0×10⁻⁸ M (∼14.5 ppb). It has a fast response time of ∼10 s and can be used for at least 2 months without any major deviation in potential. The electrode revealed very good selectivity with respect to all common alkali, alkaline earth, transition and heavy metal ions. The proposed sensor was used as an indicator electrode in potentiometric titration of lead ions and in determination of lead in edible oil, human hair and water samples. The proposed sensor was found to be superior to the best Pb²⁺-selective electrodes reported in terms of detection limit and selectivity coefficient.     

Palladium metal electrode and its analytical application to precipitation and acid–base analysis in aqueous and non-aqueous media

Electrochemical characterization of palladium electrode has been reported. The investigated electrode showed a linear dynamic response for p-toluensulfonic acid and iodide ions in the concentrations range between 5?×?10^?1 and 1?×?10^?5 mol L^?1 with a Nernstian slope of 55 mV for p-toluensulfonic acid and 63 mV per decade for iodide ions in water, as well as 53 mV for p-toluensulfonic acid and 51 mV per decade for iodide ions in dioxane. The response time of the electrodes was less than 10 s in the used solvents. Some potential analytical applications of the sensors have been pointed. Palladium electrode for the potentiometric titrations of acids (citric, barbituric, and p-toluensulfonic acid), bases (N,N’-diphenylguanidine, tributylamine, and 2,2'–bipyridine), halides, and some real samples in aqueous and non-aqueous solutions were studied. Тetrabutylammonium hydroxide, perchloric acid, and silver nitrate proved to be very suitable titrating agents for these titrations. The standard deviation of the determination of the investigated compounds was less than 0.9 % from those obtained with a glass electrode, i.e., silver electrode.     

A PVC-based 1,8-diaminonaphthalen electrode for selective determination of vanadyl ion

A PVC membrane vanadyl (VO²⁺) ion-selective electrode was constructed using 1,8-diaminonaphthalen (DAN) as a neutral carrier. The electrode shows good Nernstian response for VO²⁺ ions over a wide concentration range (1.0×10⁻¹-1.0×10⁻⁵ M). The optimum composition of the membrane was 55 wt.% poly(vinylchloride), 35 wt.% 2-nitrophenyl octyl ether (NPOE), 5 wt.% ionophore, and 5 wt.% potassium tetrakis(p-chlorophenyl)borate (KTpClPB). It has relatively fast response time and can be used at least for 5 weeks without any considerable divergence in potentials. The proposed electrode revealed relatively good selectivity for VO²⁺ over wide variety of other metal ions. The electrode was used for the potentiometric titration of VO²⁺ ions with EDTA.     

Determination of some steroidal bases in non-aqueous media by potentiometric titrations at a small constant current

In this work the volumetric and coulometric titrations of some newly synthesized androstene steroidal compounds with pyridine ring are carried out. The titrations were followed potentiometrically at a small constant current using pairs of identical platinum or glassy carbon electrodes, both in presence of quinhydrone. As the titration reagent, in volumetric titrations served 0.01 mol dm^?3 perchloric acid, and in coulometric titrations hydrogen ions were anodically generated in situ from quinhydrone at the platinum electrode. Sodium perchlorate served as the supporting electrolyte.Amounts of 1.18-5.35 mg of the investigated steroidal compounds were determined with a relative standard deviation less than 1.4% at volumetric and 1.2% at coulometric determinations. A negative influence of the supporting electrolyte on magnitude of the signal change in potentiometric determinations was observed. Glassy carbon electrodes are more advantageous over platinum ones.The achieved results are in good agreement with those of catalytic thermometric titrations.     

Solid-state ion-selective electrodes as end-point detectors in compleximetric titrations : Part II. Back-titrations in acidic media

The determination of several metal ions in the concentration range 10^-2–10^-5M by means of compleximetric back-titrations with a copper(II)-selective indicator electrode is described. The ligand, in most cases EDTA, is added in excess, which is then back-titrated with copper(II). There is good agreement between the theoretical and experimental titration curves.     

Determination of Hg(II) ions in water samples by a novel Hg(II) sensor,based on calix[4]arene derivative

A PVC membrane electrode for Hg(II) ions, based on a new cone shaped calix[4]arene (L) as a suitable ionophore was constructed. The sensor exhibits a linear dynamic in the range of 1.0 × 10^?6–1.0 × 10^?1 M, with a Nernstian slope of 29.4 ± 0.4 mV decade^?1, and a detection limit of 4.0 × 10^?7 M. The response time is quick (less than 10 s), it can be used in the pH range of 1.5–4, and the electrode response and selectivity remained almost unchanged for about 2 months. The sensor revealed comparatively good selectivity with respect to most alkali, alkaline earth, and some transition and heavy metal ions. It was successfully employed as an indicator electrode in the potentiometric titration of Hg²⁺ ions with potassium iodide, and the direct determination of mercury content of amalgam alloy and water samples.     

New Potentiometric Membrane Sensors Responsive to Pb(Ii) Based on Some Recently Synthesized 9, 10- Anthraquinone Derivatives

ABSTRACT

New potentiometric membranesensorsresponsive to Pb(II) have been developed. The membrane sensors are based on three different 9, 10-anthraquinone derivatives. The electrode based on 1, 4-bis (prop-2¹-enyloxy)-9, 10-anthraquinone exhibits a good Nernstian response for Pb(II) ions over a wide concentration range (2.5×10^?6 - 1.0×10^?2 M) with a slope of 29.8 mV decade^?1. Detection limit is 1.5×10^?6 M. The response time of the sensor is 15s and the useful working pH range is 4.7-6.8. The membrane can be used for more than 4 months without any considerable divergence in potentials. The electrodes revealed comparatively good selectivities with respect to alkali, alkaline earth and some transition and heavy metal ions. It was used as an indicator electrode in potentiometric titration of lead ions (with sulfate and oxalate ions), and for the determination of lead in waste waters.     

Anodic dissolution of the mercury electrode by the CH3O− ions formed during the reduction of organic compounds in methanol

Anodic dissolution of the HMDE from CH₃O^? ions formed during the electrochemical reduction of organic compounds in methanol arises only if the electroreduction is non-reversible. When, however, the organic substances undergo a reversible reduction, the CH₃O^? ions formed during the reduction are neutralized by the protons released during reoxidation. The anodic dissolution of the mercury electrode is attributed to the formation of insoluble Hg₂(OCH₃)₂, as with many other ions which depolarize the mercury electrode in aqueous solution with the formation of insoluble salts.     

Novel Bromide PVC‐Based Membrane Sensor Based on Iron(III)‐Salen

A novel bromide PVC‐based membrane sensor, based on iron(III)‐salen (IS) as an electroactive material, is successfully developed. The sensor possesses the advantages of low detection limit (6.0×10^?6), wide working concentration range (7.0×10^?6–1.0×10^?1 M), Nernstian behavior (slope of 59.0±0.5 mV per decade), low response time (<15 s), wide working pH range (3–9), and specially, high bromide selectivity over a wide variety of organic and inorganic anions, specially iodide, chloride, and hydroxide ions. The electrode was used in the direct potentiometric determination of hyoscine butylbromide, and as an indicator electrode in potentiometric titration of bromide ions with silver ions.