首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
The thermodynamic proton ligand and metal ligand stability constants of N-m-tolyl-p-methylbenzohydroxamic acid with Cu(II), Zn(II), Ni(II), and Mn(II) have been determined at 25° and 35° in several dioxane-water media. The pK a and logK 1 (logK 2 or log 2) varies linearly with the mole fraction of dioxane at a given temperature but not linearly with the reciprocal of dielectric constants of the medium. Values of G o, H o, and S o are tubulated. The stabilities of the complexes mostly follow the order of electron affinities of the metal ions. An attempt has been made to calculate the ligand field stabilization energy of the complexes.

Mit 2 Abbildungen  相似文献   

2.
Summary Sensitive extraction-spectrophotometric procedures are described for the complexes of Cu(II), Zn(II), Cd(II) and Hg(II) with 5-Br-PADAP using chloroform as solvent. Optimal conditions have been established for the quantitative extraction of the metal chelates and their composition and optical characteristics have been determined as well. The conditional extraction constants amount logK ex=10, the molar absorptivities of the complexes being 105 l·mole–1·cm–1. Job's method and equilibrium shift method indicate the molar ratios M5-Br-PADAP=12.
Spektralphotometrische Bestimmung von Spuren Cu(II), Zn(II), Cd(II) und Hg(II) mit 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)
Zusammenfassung Einfache und empfindliche Methoden zur extraktionsspektralphotometrischen Bestimmung von Spuren Cu(II), Zn(II), Cd(II) und Hg(II) mit 5-Br-PADAP wurden beschrieben. Chloroform wurde als Extraktionsmittel verwendet. Die optimalen Bedingungen für die quantitative Extraktion der Metallchelate wurden ermittelt und deren Zusammensetzung bestimmt. Die Stabilitätskonstanten haben hohe Werte (logK ex=10), die molare Absorption der Komplexe beträgt 1051·mol–1·cm–1. Das Molarverhältnis der Komplexe beträgt M5-Br-PADAP=12.
  相似文献   

3.
The rawpH-data, obtained from the potentiometric titrations of the titled ligands with NaOH in 75% (v/v) dioxane-water mixture performed at 20, 30 and 40°C at constant ionic strength (=0.1M-NaClO4), have been adequately corrected for dilution, and solvent effects in order to evaluate thermodynamic dissociation constants. Variance of the latter as a function of temperature has also been accounted for. The differing magnitudes of thermodynamic dissociation constants of the titled ligands have been explained on the basis of the non coplanar orientation of the phenyl ring in the ligands and a comparison has been made with those of unsubstituted benzoylacetone, dibenzoylmethane and acetylacetone.Following similar technique, thermodynamic stepwise and overall formation constants of the titled metal-ligand systems have been obtained and the results correlated with ligand basicity inverse metal crystal radii and second potentials of metals. Decrease in the free enthalpy (–G) of complexation reaction has also been evaluated.
Untersuchung der Gleichgewichte von Mn(II), Mg(II), Ca(II), Sr(II) und Ba(II) mit p-Fluor-, p.-Chlor-, p-Brom-, p-Methyl-benzoylaceton und 1-(4-Fluorphenyl)-1,3-pentanedion
Zusammenfassung Aus der potenitometrischen Titration der Titelverbindungen mit NaOH in 75 (v/v) Dioxan—Wasser bei, 20, 30 und 40°C bei konstanter Ionenstärke (=0,1M-NaClO4) wurden die thermodynamischen Dissoziationskonstanten ermittelt. Verdünnungs-, Lösungsmittel-und Temperatureffekte wurden berücksichtigt. Die unterschiedlichen Dissoziationskonstanten werden mit der Nichtplanarität des Phenylrings in den Liganden erklärt. Außerdem wurden die Komplexbildungskonstanten bestimmt; sie sind in die Diskussion miteinbezogen.
  相似文献   

4.
The stability constants of ternary complexes of theMAL type have been determined for Cu(II), Zn(II) and Cd(II). The ligands chosen for this study belong to the biologically important ones viz. Bipyridyl (A) and Nitrilotriacetic acid (L). LogK MAL values for Cu(II), Zn(II) and Cd(II) are 11.42, 10.67 and 9.72, respectively, at temp.=25°C and =0.1M (KNO3); the order is discussed.
Ternäre Komplexe in Lösung: Die Komplexibildung zwischen Kupfer(II), Zink(II) und Kadmium(II) mit Liganden von biologischem Interesse
Zusammenfassung Die Stabilitätskonstanten für Cu(II)-, Zn(II)- und Cd(II)-Komplexe vom TypMAL wurden bestimmt. Die biologisch relevanten Liganden, die für diese Untersuchung ausgewählt wurden, waren Bipyridyl (A) und Nitrilotriessigsäure (L). Bei einer Temperatur von 25°C und =0,1M (KNO3) sind die entsprechenden logK MAL -Werte für Cu(II), Zn(II) und Cd(II) 11,42, 10,67 und 9,72; diese Reihenfolge wird ebenfalls diskutiert.
  相似文献   

5.
Extraction of Hg(II), Se(IV), Mn(II) and Co(II) has been carried out with 1-phenyl-3-methyl-4-trifluoroacetyl-2-pyrazolin-5-one (HPMTFP) and triphenylphosphine oxide (TPPO) into chloroform from pH 1–10. Quantitative extraction of Hg(II), Mn(II) and Co(II) at pH 4 with equimolar 0.05M (PMTFP+TPPO) in chloroform was observed. Se(IV) remains unextracted at this pH range. The stoichiometric composition of the extracted complexes M(PMTFP)2·nH2O (M=Mn, Hg), M(PMTFP)2·2TPPO (M=Mn and Co) and Co(PMTFP)2·TPPO·H2O at less than 0.1M TPPO has been established. The formation constantsK m,0 andK m,n and stability constants m,n have been computed. The analytical method developed was applied to the IAEA standard reference material (SRM) potato fluor V-4 for the determination of these elements using NAA technique.  相似文献   

6.
The crystal structures of the two derivatives of aminomethane-1,1-diphosphonic acid with morpholinyl- (1) and thiomorpholinyl- (2) side chains were determined by single crystal X-ray diffraction and discussed with respect to molecular geometry and solid state organization. The protonation equilibria, solution behavior and complex-formation equilibria in solutions of 1 and 2 with the Zn(II), Mg(II) and Ca(II) ions were studied by means of NMR, pH-potentiometry and ESI-MS methods.As the pK(NH+) protonation constants of 1 and 2 are high (11.65 and 11.91, respectively) two different approaches were used to evaluate the pH-potentiometric data. The first approach disregarded the proton-dissociation from the NH+ group. In the second one, all the pKa values were considered in the M(II):ligand formation equilibria. For 1, the accuracy of the pK(NH+) determination was shown to be sufficient to calculate reliable stability constants of metal complexes with the use of both approaches. For 2, only approach neglecting the pK(NH+) protonation constant was shown to be correct.The studied acids form dinuclear, [M2L3Hx], [M2L2Hx] and mononuclear MLHx and ML2Hx complexes with different degree of ligand protonation. Tendency to undergo some oligomerization with the increase in the metal and ligand concentration was demonstrated for the [CaLH] complex of 1 and 2. As far as 1 and 2 remain protonated, the Zn(II), Mg(II) and Ca(II) ions are coordinated exclusively through oxygen atoms of the phosphonate groups. The metal promoted proton dissociation from the NH+ ring atom takes place in alkaline pH.  相似文献   

7.
以HMFC[(反)-肉桂酰基二茂铁缩(S)-甲基二硫代碳酰腙]与HBFC[(反)-肉桂酰基二茂铁缩(S)-苄基二硫代碳酰腙]两种Schiff碱分别与醋酸镉[Cd(OAc)2•2H2O]、醋酸汞[Hg(OAc)2]反应, 合成了6个未见文献报道的配合物Cd(MFC)2•H2O, Cd(MFC)•OAc, Cd(BFC)2, Hg(MFC)2, Hg(MFC)•OAc, Hg(BFC)2, 考察了其物理性质, 并利用元素分析、IR, 1H NMR及摩尔电导表征了其组成、可能结构, 推断了配位过程. 结果表明: 这两种Schiff 碱都是反式双齿配体, 经烯硫醇化并失去质子后, 以负硫离子与过渡金属离子形成共价键, 氮原子与中心金属离子形成配位键.  相似文献   

8.
The complexation tendencies of N,N-di-(-hydroxyethyl)-dithiocarbamic acid [DEADTCH, (CH2CH2OH)2NCSSH] towards a large number of metal ions have been examined. The complexes formed with transition and post-transition metal ions in slightly acidic and neutral solutions have the general formulaM(DEADTC) x, wherex is the valence state of the metal,M=Cr(III), Fe(III), Co(III), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Tl(I), and Tl(III). In addition the interesting mixed ligand complex ClHg(DEADTC) was prepared. These complexes have been characterised through X-ray, magnetic, conductance and spectral (UV and IR) measurements.  相似文献   

9.
Summary Complexes of nickel(II), palladium(II), copper(II), cobalt(II), and cobalt(III) with methyl-2-(-salicylaldiminoethyl)-cyclopent-1-en-dithiocarboxylate (H2L1) and methyl-2-(-salicylaldiminoisopropyl)cyclopent-1-en-dithiocarboxylate (H2L2) have been prepared. They contain the donor sites ONNS. The metal(II) ions from neutral, monomeric square planar chelate complexes. The cobalt(III) complexes [CoL1-(H2O)2]X (X=Cl or ClO4) appear to betrans-diaqua-species. All compounds have been characterized by a number of physico-chemical methods.  相似文献   

10.
The kinetics of the reaction of oximate ions with 2,4-dinitrophenyl p-toluenesulfonate, 4-nitrophenyl p-toluenesulfonate, diethyl 4-nitrophenyl phosphate, and ethyl 4-nitrophenyl ethylphosphonate in H2O-DMSO mixtures (0 to 95 vol % of DMSO) cannot be described in terms of a single Bro/nsted equation. Regardless of the nature of the reaction center and leaving group, both in water and in 80% DMSO fast leveling of the reactivity of oximate ions is observed, the -effect decreases at pK a 9.0 and disappears at pK a 12.0 owing to difference in the solvation of weakly (pK a 9.0) and strongly basic (pK a 9.0) oximate ions rather than to change of the transition state. Just unfavorable solvation effects are responsible for the fact that the limiting nucleophilic reactivity of oximate ions (as typical -nucleophiles) is not higher than the reactivity of strongly basic alkoxide ions.  相似文献   

11.
Incorporation of pH correction, in data obtained from the potentiometric titration of p-fluorobenzoylacetone with NaOH solution in dioxane-water (31,V/V) at 30±0.1°C in a medium of constant ionic strength, =0.1M (NaClO4) gave the value of thermodynamic dissociation constant (pk D ) as 12.06±0.02. Under similar conditions of solvent composition, temperature and ionic strength the thermodynamic stepwise formation constants of the complexes formed between Ni(II), Co(II), Zn(II) and Cd(II) ions and the above ligand, using method of least squares, gave log 2 as 19.50±0.05, 18.89±0.05, 18.61±0.04 and 16.16±0.08 resp. This order is in accordance with theIrving-Williams series. Derivatives of the above metals have also been synthesised and characterised.With 2 Figures  相似文献   

12.
The analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III) and 1 M H2SO4 are investigated using the polarographic technique. The wave corresponding to the reduction of Fe(III) to Fe(II) was found to be completely suppressed by the addition of 1% pyrogallol. Thus, different mixtures of these elements, viz. Hg(II), Cu(II), Cd(II), As(III) and Fe(III)-mixture (A), Cu(II), Cd(II), Sb(III), As(III) and Fe(III)-mixture (B), and Cu(II), Cd(II), Ti(IV), U(VI) and Fe(III)-mixture (C), were quantitatively determined using 1% pyrogallol and 1 M H2SO4 as supporting electrolyte. The i1/c results give excellent correlations in each case, as indicated from the results of leastsquares regression analysis.  相似文献   

13.
Recently, one of the most common conditions that manifests as joint and muscle inflammation is rheumatoid arthritis. One of the treatments for this arthritis includes non‐steroidal anti‐inflammatory drugs (NSAIDs) of the oxicam family, and the widest used drug in this family is tenoxicam (Tenox). In this study, the complexation properties of the drug Tenox with Ca(II), Sr(II) and Ba(II) ions in a (dichloromethane + water) binary solvent system are reported. The formed metal complexes were characterized structurally, thermally, and biologically. Tenox was found to act as a chelate monoanionic ligand towards all metal ions with complexation stoichiometry of 1:2 (Metal: Tenox) for Ca(II) and Sr(II) ions, and 1:1 for Ba(II) ions. The Tenox ligand behaves as a bidentate ligand when coordinated with Sr(II) or Ba(II) ions and as a tridentate ligand when coordinated with Ca(II) ions. The Sr(II) and Ba(II) complex of the Tenox ligand exhibited marked inhibitory effect on the cell growth of the C. albicans species.  相似文献   

14.
The competitive sorption of Cu(II), Eu(III) and U(VI) ions in aqueous solutions by TiO2, has been investigated by potentiometry at I = 0.1 M NaClO4, 25 °C and under atmospheric conditions. For Cu(II) ions the investigation was performed directly by means of a Cu2+ ion selective electrode, whereas for the Eu(III) and U(VI) ions indirectly based on competition reactions between the Cu(II) ion and the Eu(III) and U(VI) ions. Numerical analysis of the experimental data supports the formation of inner-sphere surface complexes and allows the evaluation of the formation constant of the (TiO)2Cu, which is found to amount to log β* = 4.3 ± 0.4. Addition of competing Eu(III) and U(VI) ions in the aqueous system leads to replacement of the Cu(II) by the competitor metal ion. Evaluation of the potentiometric data obtained from competition experiments indicates on an ion exchange mechanism. The formation constant of the Eu(III) and U(VI) species adsorbed on TiO2 is found to be log β* = 4.4 ± 0.7 and 4.8 ± 0.8, respectively. The relative affinity of the TiO2 surface for the metal ions under investigation is U(VI) > Eu(III) > Cu(II).  相似文献   

15.
Equilibria occurring between glycine (L) and magnesium(II) and calcium(II) were studied by measuring at 25 °C the electromotive force (e.m.f.) of the cell: (–) Pt, H2/SolutionS/R.E. (+) where R.E. is the reference electrode described in the text.Equilibria taking place in solutions containing iron(II) and glycine were investigated by means of the cell: (–) R.E./SolutionS/G.E. (+) where G.E. is the glass electrode. The general composition of solutionS was in both cases the following: B M inM 2+;H M in H+;A M inL; 3.00M in ClO 4 ; (3-H-2B)M in Na+.Experimental data were explained by assuming the existence of the species:: MgL(log 1,0,1=1.53±0.05); MgL 2(log 2,0,1=2.26±0.05); CaL(log 1,0,1==0.75±0.03); FeL(log 1,0,1=4.20±0.04).Protonation constants of aminoacetate, not known in the experimental conditions selected, were determined by means of e.m.f. measurements carried out with a H2 electrode.
Komplexbildung zwischen Glycin und Magnesium(II), Calcium(II), bzw. Eisen(II) bei 25 °C in 3,00M NaClO4
Zusammenfassung Die Gleichgewichte zwischen Glycin (L) und Magnesium(II) bzw. Calcium(II) wurden bei 25 °C durch E.M.K. Messungen der folgenden Meßkette untersucht: (–) Pt, H2/ProbenlösungS/R.E. (+) wobei R.E. Referenz-Elektrode bedeutet (siehe Text).Zum Studium der Reaktion zwischen Eisen(II) und Glycin bei 25 °C wurde folgende Meßkette benutzt: (–) R.E./ProbenlösungS/G.E. (+) wobei G.E. Glas-Elektrode bedeutet.Alle Meßproben hatten die folgende allgemeine Zusammensetzung:B M inM 2+;H M in H+;A M inL; 3,00M in ClO 4 ; (3-H-2B)M in Na+.Die experimentellen Daten konnten unter Annahme folgender Komplexe erklärt werden: MgL(log 1,0,1=1,53±0,05); MgL 2(log 2,0,1=2,26±0,05); CaL(log 1,0,1=0,75±0,03); FeL(log 1,0,1=4,20±0,04). Die Protonierungskonstanten von Aminoacetat, die bei den gewählten experimentellen Bedingungen nicht bekannt sind, wurden mittels E.M.K. Messungen (mit Wasserstoff-Elektrode) bestimmt.
  相似文献   

16.
The coupled transport of Cu(II), Cd(II) and Ni(II) ions through a bulk liquid membrane (BLM) containing pyridine-2-acetaldehyde benzoylhydrazone (2-APBH) as carrier dissolved in toluene has been studied. Once the optimal conditions of extraction of each metal were established, a comparative study of the transport kinetics for these metals was performed by means of a kinetic model involving two consecutive irreversible first-order reactions. The kinetic parameters (apparent rate constants of the metal extraction and re-extraction reactions (k 1, k 2), the maximum reduced concentration of the metal in the liquid membrane (), the time of the maximum value of R o ( t max) and the maximum entry and exit fluxes of the metal through the liquid membrane ( and ) of the extraction and stripping reactions were evaluated and results showed good agreement between experimental data and theoretical predictions. Complete transport through the membrane took place according to the following order: Cd(II)>Cu(II)>Ni(II), with similar kinetic parameters obtained for Cu(II) and Cd(III). The transport behaviour of Ni(II) was different to that of Cu(II) and Cd(III), probably due to the different stoichiometry of the nickel complex compared to those of the other metal ions and the different chemical conditions required for its formation. The influence of the sample salinity on the transport kinetics was studied. k 1 values decreased slightly when the feed solution salinity was increased for Cu(II) and Ni(II), but not for Cd(II). Values of k 2 were practically unaffected. The proposed BLM was applied to the preconcentration and separation of metal ions (prior to their determination) in water samples with different saline matrices (CRM, river water and seawater), and good agreement with the certified values was obtained.  相似文献   

17.
This paper describes the preparation of zwitterion-functionalized polymer microspheres (ZPMs) and their application to simultaneous enrichment of V(V), Cr(III), As(III), Sn(IV), Sb(III) and Hg(II) from environmental water samples. The ZPMs were prepared by emulsion copolymerization of ethyl methacrylate, 2-diethylaminoethyl methacrylate and triethylene glycol dimethyl acrylate followed by modification with 1,3-propanesultone. The components were analyzed by elemental analyses as well as Fourier transform infrared spectroscopy, and the structures were characterized by scanning electron microscopy and transmission electron microscopy. The ZPMs were packed into a mini-column for on-line solid-phase extraction (SPE) of the above metal ions. Following extraction with 40 mM NH4NO3 and 0.5 M HNO3 solution, the ions were quantified by ICP-MS. Under the optimized conditions, the enrichment factors (from a 40 mL sample) are up to 60 for the ions V(V), As(III), Sb(III) and Hg(II), and 55 for Cr(III) and Sn(IV). The detection limits are 1.2, 3.4, 1.0, 3.7, 2.1 and 1.6 ng L?1 for V(V), Cr(III), As(III), Sn(IV), Sb(III) and Hg(II), respectively, and the relative standard deviations (RSDs) are below 5.2%. The feasibility and accuracy of the method were validated by successfully analyzing six certified reference materials as well as lake, well and river waters.
Graphical abstract Zwitterion-functionalized polymer microspheres (ZPMs) were prepared and packed into a mini-column for on-line solid-phase extraction (SPE) via pump 1. Then V(V), Cr(III), As(III), Sn(IV), Sb(III) and Hg(II) ions in environmental waters were eluted and submitted to ICP-MS via pump 2.
  相似文献   

18.
Zusammenfassung Acenaphthenchinon-(2-hydroxy)-anil (AMHA) eignet sich zur Chelatbildung mit folgenden Metallionen in wäßriger, Soda- und Natronlauge enthaltender Lösung: Ag, Hg(I), Hg(II), Pb(II), Cu(II), Cd, M, Co und Ca. Das Calciumchelat läßt sich mit Chloroform extrahieren. Bei Einhaltung bestimmter Konzentrationen von Na2CO3 und NaOH ist diese Reaktion bei Abwesenheit sonstiger komplexbildender Ionen für die quantitative Bestimmung von 10 bis 120g Ca geeignet.
Summary Acenaphthenequinone-(2-hydroxy)-anil (AMHA) is suitable for chelate formation with the following metal ions in aqueous solution containing sodium carbonate and sodium hydroxide: Ag, Hg(I), Hg(II), Pb(II), Cu(II), Cd, Ni, Co, and Ca. The calcium chelate can be extracted with chloroform. If the concentrations of Na2CO3 and NaOH are kept within certain limits, the reaction is suitable, in the absence of other complex-forming ions, for the quantitative determination of 10 to 120g Ca.
  相似文献   

19.
The title compound, trimercury(II) bis­[selenite(IV)] selen­ate(VI), contains three crystallographically inequivalent HgII cations with coordination numbers of eight (denoted Hg1 and Hg2) and five (denoted Hg3). The corresponding coordination polyhedra around the metal atoms might be described as intermediates between a square antiprism and a triangulated dodecahedron for both Hg1 and Hg2, and a strongly distorted truncated octahedron for Hg3. [HgO8/2] layers of edge‐sharing [HgO8] polyhedra propagate parallel to the bc plane, and are connected via SeVIO4 tetrahedra and [Hg3O5] polyhedra along the a axis, forming an arrangement with channels propagating parallel to the b axis. The two independent SeIVO3 pyramids bridge the Hg atoms, and the non‐bonding orbitals of the SeIV ions protrude into the channels from opposite sides.  相似文献   

20.
A new series of cobalt(II, III) and copper(II) complexes of 3-(2-furylidene) hydrazino-5,6-diphenyl-1,2,4-triazine (L) having formulae LMIIX2, L2MIIX2 and LCoIIIX3, (X = Cl, OAc or ClO4; MII = CoII or CuII) were isolated and characterized by elemental analyses, molar conductances, magnetic moments and i.r., electronic and e.s.r. spectral measurements. The i.r. spectra indicated that the ligand, L, behaves as a neutral bidentate towards divalent metal ions via a triazine-N, and azomethine-N, and acts as a tridentate towards cobalt(III) via the same two nitrogen atoms and the furan-O. The magnetic moments and electronic spectral data suggest a pseudo-tetrahedral geometry for [L2Co]Cl2, a diamagnetic tetragonally distorted octahedral geometry for [LCoCl3], [LCo(OAc)3] · 4H2O and [LCo(H2O)3](ClO4)3 and a dimeric square pyramidal geometry for both [LCuCl2] and [LCu(OAc)2] · 2H2O through bridged chloro and acetato ligands, respectively. The ligand field parameters (B, 10Dq and ) were evaluated from the electronic spectral data and magnetic moments and related to the bonding of the complexes. The X-band e.s.r. spectra showed three g values with large magnetic anisotropy for [L2Co]Cl2 in accordance with pseudo-tetrahedral CoII complexes; axial pattern for [LCuCl2], [LCu(OAc)2] · 2H2O and [L2Cu(H2O)2](ClO4)2 with two g values and a signal due to M s = ±2 transition for both chloro and acetato copper(II) complexes.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号