On Mn(Hg)/Mn(II) equilibria and reactions in aqueous solution

The title subject has been studied through galvanostatic single-pulse and chronopotentiometric measurements on the Mn(Hg)/Mn(II) electrode and equilibrium measurements on the same and the Ag/AgCl electrode, all in x MMnCl₂+(0.5?x)M MgCl₂ solutions of pH 4.3–4.9 at 25°C. The Mn(Hg)/Mn(II) reactions are found to occur in two consecutive steps, an unsymmetric (α_c near 0.8) ion-transfer step Mn(Hg)/Mn(I) and an essentially symmetric (α_c near 0.5) electron-transfer step Mn(I)/Mn(II). Besides charge transfer, no sluggishness other than diffusion is observed, but the dispersed precipitate Mn₂Hg₅ of saturated amalgam serves as an ageing-dependent source of anodic reactant Mn(Hg). Quantitative kinetic and thermodynamic data are presented and discussed. Comparisons are made to corresponding reactions for the succeeding elements iron, cobalt, nickel, copper, and zinc.     

Single-ion activities and Zn/Zn(II) reactions in alkali chloride solutions

The title subject has been studied through equilibrium potential measurements on the Zn/Zn(II) and the Ag/AgCl electrode vs. SCE and galvanostatic single-step and chronopotentiometric polarization measurements on the former electrode, all in acidified (to pH about 3) solutions of 0.005 M ZnCl₂+0.99 M MeCl (for Me=Li, Na, K, and Cs) at 25°C. It is found that the Zn(II) activity decreases together with the alkali-ion activity along the sequence LiCl>NaCl>KCl>CsCl, that the chloride-ion activity essentially is insensitive to mutual substitutions of alkali ions, and that the Zn/Zn(II) reactions exhibit no other than pure activity effects of such substitutions. The results support that the Zn/Zn(II) electrode reacts in two consecutive steps with Zn(I) as intermediate, and that some sluggishness appears in chemical reactions to and from electroactive Zn(II) species.     

Effect of ammonia on the Zn(Hg)/Zn(II) electrode reactions in aqueous chloride solutions

The title subject has been studied using single pulse and chronopotentiometric polarization measurements on the Zn(Hg)/Zn(II) electrode and equilibrium measurements on the same and the Zn/Zn(II) electrode, mainly in 2 M NH₄Cl with 0–0.3 M NH₃. At low ammonia concentrations, the Zn(Hg)/Zn(II) reactions are found to occur in two consecutive charge-transfer steps with Zn(I) as intermediate, and with little or no participation of ammonia. At higher ammonia concentrations, however, nearly symmetric transfer by divalent zinc ion (α=0.5 and n=2) to and from diammine species appears to be the predominant charge-transfer step.     

On Cu(Hg)/Cu(II) equilibria and reactions in aqueous sulphate solution

Combined thermodynamic and kinetic studies have revealed amalgam properties, solution activities, and diffusion data besides charge-transfer parameters and exchange rates for either step of the Cu(Hg)/Cu(II) electrode in aqueous solutions of xM CuSO₄+(0.5?x) M MgSO₄+H₂SO₄ (to pH about 2.5) at 25°C. The studies allow separation of mean ionic activities into convenient single-ion ones. The kinetic results demonstrate the consecutive two-step mechanism involved. Comparison is made to the solid Cu/Cu(II) electrode, and double-layer effects are discussed.     

Effect of alkali cations,halides and thiocyanate on the Mn(Hg)/Mn(II) electrode reactions

The title subject has been studied by galvanostatic single-pulse, chronopotentiometric and equilibrium measurements on the Mn(Hg)/Mn(II) electrode (mainly saturated managanese amalgams) in one molar alkali chloride (LiCl, KCl and CsCl) and potassium iodide and thiocyanate solutions of pH 4 to 5 at 25°C. The Mn(Hg)/Mn(II) reactions are found to occur in two consecutive steps with monovalent ions as intermediate in all these solutions. The rates of both the ion-transfer step Mn(Hg)/Mn(I) and the electron-transfer step Mn(I)/Mn(II) appear independent of the cations Li⁺ and K⁺ and of the anions Cl^?, I^? and SCN^?, when differences in bulk activities of electroactive species are corrected for. The Cs⁺ ion, however, seems to retard the reactions more than expected from bulk activity changes, and this can be explained by Cs⁺ specific adsorption or by variations in the properties of the inner layer with the cation.     

Kinetics of the Zn(II)/Zn(Hg) electrode reactions in DMSO solutions of halide ions

The electrode reaction Zn(II)/Zn(Hg) in complex chloride, bromide, and iodide solutions with DMSO as solvent and ammonium perchlorate as supporting electrolyte has been studied at the equilibrium potential by the faradaic impedance method and a square-wave method. Furthermore, double-layer data have been determined by electrocapillary measurements. The results indicate that the zinc chloride and bromide complexes do not contribute noticeably to the exchange current density, while in the iodide system both the solvated zinc ion and the first complex take part in the charge transfer. From the dissimilar results valid for water and DMSO solutions the conclusion is made that probably ligand bridging at the amalgam by the halide ions is operative in water solutions, whereas in DMSO the larger solvent molecules adsorbed can form a steric hindrance to ligand bridging by chloride or bromide ions.     

Triazine based Mn (II) and Mn (II)/Ln (III) complexes: Synthesis,characterization and catecholase activities

In the current work, two triazine‐based multidentate ligands (H₂L¹ and H₂L²) and their homo‐dinuclear Mn (II), mononuclear Ln (III) and hetero‐dinuclear Mn (II)/Ln (III) (Where Ln: Eu or La) complexes were synthesized and characterized by spectroscopic and analytical methods. Single crystals of a homo‐dinuclear Mn (II) complex {[Mn (HL¹)(CH₃OH)](ClO₄·CH₃OH}₂ ( 1 ) were obtained and the molecular structure was determined by X‐ray diffraction method. In the structure of the complex, each Mn (II) ion is seven‐coordinate and one of the phenolic oxygen bridges two Mn (II) centre forming a dimeric structure. The UV–Vis. and photoluminescence properties of synthesized ligands and their metal complexes were investigated in DMF solution and the compounds showed emission bands in the UV–Vis. region. The catecholase enzyme‐like activity of the complexes were studied for 3,5‐DTBC → 3,5‐DTBQ conversion in the presence of air oxygen. Homo‐dinuclear Mn (II) complexes ( 1 and 4 ) were found to efficiently catalyse 3,5‐DTBC → 3,5‐DTBQ conversion with the turnover numbers of 37.25 and 35.78 h^?1 (k_cat), respectively. Mononuclear Eu (III) and La (III) complexes did not show catecholase activity.     

Cu(II)-Cu(Hg)体系在蔗糖水溶液中的电化学行为

糖及其聚合物有着重要的生理功能,研究它们的热力学性质具有重要的意义[1 5]。本文考察Cu(II)在蔗糖水溶液中的电化学行为,获得了一些重要信息。1　实验部分使用试剂均为分析纯。蔗糖(北京化学试剂总厂)在343K时真空干燥6h。LiClO4(上海化学试剂总厂)在403K时减压干燥后保存在干燥器中。硝酸铜(北京化学试剂总厂)。所用溶液均采用重量法用二次蒸馏水配制。配好的溶液测定前用通过焦性没食子酸溶液的氮气来除氧。测定温度为298±1K。极谱和伏安测定在微机电化学分析系统(LK98A型)上进行,该机由天津市兰力科化学电子高技术有限公司制…     

Kinetics of the Hg(II)/Hg electrode reaction in DMSO solutions of chloride ions

The electrode reaction Hg(II)/Hg in complex chloride solutions with dimethyl sulfoxide as solvent has been investigated at the equilibrium potential by the faradaic impedance method and a cyclic current-step method. The ionic strength was 1 M with ammonium perchlorate as supporting electrolyte, and the temperature was 25°C. Double-layer data have been determined by electrocapillary measurements. From the results of the kinetic measurements at ligand numbers ≤1.1 or ≥2.3 it is concluded that the overall charge transfer proceeds step-wise. The solvated Hg²⁺ and Hg₂²⁺ as well as the complexes HgCl_j^2?j and the dinuclear Hg₂Cl³⁺ contribute to the exchange current density. The rate constant of the step HgCl_j^2?j/ Hg(I) is found to increase with the number of Cl^? coordinated. This increase can be correlated to a decrease in solvation and a lengthening of the Hg?Cl distance. For 1.1 << 2.3, impedance measurements indicate a rate-controlling adsorption step. It is suggested that the uncharged HgCl₂ then forms an adsorbed network on the mercury surface.     

Selective fluorescent Hg(II) detection in aqueous solutions with a dye intermediate

A dye intermediate, 1-amino-8-naphthol-3,6-disulfonic acid sodium (ANDS) was first used to selectively recognize Hg(II) in aqueous solutions with its fluorescence being strong quenched. The fluorescence quenching of ANDS was attributed to the formation of an inclusion complex between Hg(II) and ANDS by 2:1 complex ratio (K=6.2 x 10(9)), which has been utilized as the basis of the fabrication of the Hg(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed chemosensor were investigated. The sensor shows a linear response toward Hg(II) in the concentration range 2.9 x 10(-6) to 5.5 x 10(-5)M with a limit of detection of 5.3 x 10(-7)M, and a working pH range from 5.0 to 9.0. It shows excellent selectivity for Hg(II) over a large number of cations such as alkali, alkaline earth and transitional metal ions. The proposed method was utilized successfully for the detection of Hg(2+) in water samples.     

Effect of halides and alkali cations on the Zn(Hg)/Zn(II) electrode reactions

The title subject has been studied by galvanostatic single-pulse, chronopotentiometric and equilibrium measurements on the Zn(Hg)/Zn(II) electrode in x M KI+(1?x) M KCl (x from 0 to 1), 1 M KBr and 1 M MeCl (Me=Li, Na, K and Cs) solutions of pH 3 at 25°C. Quantitative information about the effect of specifically adsorbed halides on the rates of the Zn(II)/Zn(I) and the Zn(I)/Zn(Hg) steps is obtained separately (for the latter step mainly at potentials near ?1.0 V(SCE)), and the latter step seems to be more influenced than the former by the adsorption. An attempt is made to correlate the adsorption effect on the rate of the Zn(II)/Zn(I) step to double-layer parameters according to recent models for such effects. The extra current observed at potentials where the halides are adsorbed, seems to vary with the surface activity of the specifically adsorbed ion. The lack of any observed kinetic effect of Cs⁺, which is specifically adsorbed at these potentials, is possibly due to the Cs⁺ specific adsorption enhancing the Cl^? specific adsorption and vice versa, so that the decelerating and accelerating effects by these ions may cancel each other.     

Kinetics and mechanism of the Cu(I)/Cu(Hg) electrode reactions in DMSO solutions of halide ions

The electrode reaction Cu(I)/Cu(Hg) in complex chloride, bromide and iodide solutions with DMSO as solvent has been studied at the equilibrium potential by the faradiac impedance method and a cyclic current-step method. The kinetic data refer to the ionic strength 1 M with ammonium perchlorate as supporting electrolyte and to the temperature 25°C. Double-layer data have been obtained from electrocapillary measurements. From the results for the chloride system at [Cl^?]>15 mM it is concluded that the charge transfer is catalysed by ligand bridging at the amalgam and the following parallel reactions predominate: Cl_ads^?-Cu⁺+e^?(am)Cl_ads^?+Cu(am) Cl_ads^?-Cu₂Cl_j^2?j+e^?(am)Cl_ads^?+Cu(am)+CuCl_j^1?j At lower [Cl^?] and in the whole ligand concentration range available in the bromide and iodide systems the impedance measurements indicate a rate-controlling adsorption step. It is suggested that uncharged complex CuL (L^?=halide ion) then forms an adsorbed two-dimensional network on the amalgam surface.     

Selective separation of Hg(II) from aqueous solutions by the precipitate flotation technique

Summary The flotation of Hg(II) ions as sulphide or iodide from aqueous solutions has been investigated, using oleic acid as surfactant. Selective separation from Cd ions has been achieved. There was no interference by Bi, Pb, Cu, Cd, Mn, Zn, Co or Ni.     

Spurenbestimmung von Hg(I)/Hg(II) oder Hg(0)/Hg(I) nebeneinander sowie indirekte Bestimmung von Hg-komplexierenden Anionen mit dem Kaltdampf-AAS-Verfahren

Zusammenfassung Die Anwendung des Kaltdampf-Verfahrens für die Speziesanalyse des Quecksilbers wurde untersucht. Wechselwirkungen von Hg(II) mit Hg(0) zu Hg(I) und mit komplexierenden Anionen machen folgende Bestimmungen möglich: Hg(II) und Hg(I) nebeneinander, Hg(0)-Gehalt der Luft sowie neben Hg(I) und Quecksilberkomplexierende Anionen. Die Verfahren beruhen darauf, daß Hg(II) infolge Synproportionierung ein Entweichen des Hg(0) in den Gasraum unterdrückt. Erst nach Komplexierung des Hg(II) ist dies möglich. Im Signalverlauf der Extinktionskurve sind zwei Punkte maßgebend: Aus dem Offsetpunkt ergibt sich der Gehalt an Hg(II) und aus der Extinktion die Hg(I)-Menge. Das Verhältnis von Hg(II)Hg(I) muß mindestens 21 betragen. Die Bestimmungsgrenze liegt im ppb-Bereich.

---

Simultaneous trace determination of Hg(I)/Hg(II) or Hg(0)/Hg(I) and indirect determination of mercury complexing anions by means of cold-vapor-AAS

Summary The employment of the cold-vapor AAS for the species analysis of mercury has been tested. Interactions of Hg(II) with Hg(0) to Hg(I) on the one hand and with complexing anions on the other hand allow the following determinations: Hg(II) and Hg(I) in the same solution, Hg(0) in the air and in the presence of Hg(I), mercury complexing anions in a solution. The procedure depends on the fact that Hg(II) represses the vaporization of Hg(0) as a consequence of synproportionation.The vaporization is only possible after complexing the Hg(II). Two points of the absorption curve are important: the point of offset allows the calculation of Hg(II) and the absorption is proportional to the quantity of Hg(I). The ratio of Hg(II)Hg(I) has to be 21 (minimum). The determination limit is at the ppb-level.