Determination of Formation Constants of Co￣(2+), Ni￣(2+),Cu￣(2+) and Zn￣(2+) Complexes with Humic and Fulvic Acidsby Potentiometric Titration Method

The formation constants of Co￣(2+), Ni￣(2+), Cu￣(2+) and Zn￣(2+) complexes with humic acid (HA) and fulvicacid (FA) in red soil were determined by the potentiometric titration method. The constants as a functionof composition of the complexation solutions were obtained by two graphical approaches respectively Theformation constants decreased with increasing concentration of metal in the solution. The results provideunambiguous evidence for the heterogeneity of the function groups of humic substances. The formationconstants of FA were much smaller than those of HA, and the formation constants of Cu￣(2+) were muchgreater than those of Co￣(2+) , Ni￣(2+) and Zn￣(2+) . The potentiometric titration method for determining formationconstants are also discussed in the article.

DETERM INATION OF THE STABILITY CONSTANTS OF COMPLEXES OF HISTIDINE,SOME DIPEPTIDES AND TRIGLYCINE WITH Zn(Ⅱ)AND Cd(Ⅱ)USING SMALL-SCALE PH-METRIC TITRATIONS

A potentiometric study on the complexes of His,Gly-His,ALa-His,Gly-Gly and Gly—Gly—Gly with Zn(Ⅱ)and Cd(Ⅱ)has been reported.Small-scale potentiometric titrations were car- ried out to determine stabil ity constants of complexes at 25℃ with I=0.10 mol dm^(-3)(KNO_3).The com- puter programs SUPERQUAD were applied for data treatment with satisfactory results.

A COMPARISON OF THE DETERMINATION OF STABILITY CONSTANTS OF COMPLEXES OF Cd(Ⅱ)WITH AMINO ACIDS AND SIMPLE PEPTIDES USING MICRO—pH—METRIC TITRATIONS AND CYCLIC VOLTAMMETRY

This paper reports the determination of stability constants for complexes of Cd(Ⅱ)with Gly, Ala,Val,Asp,Gly—Asp,Asp Gly,Gly—Gly and Gly—Gly—Gly using both micro—pH—metric titra- tions and the application of convolution—deconvolution cyclic voltammetry at 25℃ and I=0.10 mol· dm^(-3)(KNO_3).Stability constants were calculated from pH—metric data using the SUPERQUAD com- puter program and cyclic voltammograms were collected,stored and manipulated using the EG and G CONDECON 300 software.A considerably larger ligand:metal ratio(e,g.50:1)was possible using voltammetry.Evaluation of results from the two techniques suggests that stability constants for the species[CdL_2]and[CdL_3]are reliable when calculated fromvoltammetry while those for[CdL]are more reliable when determined by pH-metric titration.

A comparison of the determination of stability constants of complexes of Pb(II) with amino acids using micro-pH-metric titrations and cyclic voltammetry

This paper reports the determination of stability constants for complexes of Pb(Ⅱ) with Gly, Ala, Asp and Gly-Gly using both micro-pH-metric titrations and the application of convolution-de- convolution cyclic voltammetry at 25℃ and I = 0.10 mol.dm^(-3)(KNO_3). Stability constants were calculated from pH-metric data using the SUPERQUAD computer program and cyclic voltammograms were collected, stored and manipulated using the E G and G CONDECON 300 software. A consider- ably larger ligand: metal ratio (e.g. 50:1) was possible using voltammetry. Under these conditions, hydroxy complex formation was minimised and the formation of bis-complexes optimised. Computer based calculations were carried out on PC-compatible microcomputers fitted with mathematics co- processors. Evaluation of results from the two techniques suggests that stability constants for the species [PbL_2] are reliable when calculated from voltammetry while those for [PbL] are mote reliable when determined by pH-metric titration.

Linear free energy relationships between reaction rate constants and equilibrium constants of complex compounds——III. Kinetics and mechanisms of ternary complex formation between (5-X-1, 10-phenanthroline)copper(II) and threonine

The kinetics of ternary complex formation involving Cu(5-X-1, 10-phen) and threonine (CuAL, A=5-X-1, 10-phen; L=threonine or represented by O-N; X=NO_2, Cl, H, CH_3) has been studied by temperature-jump and stopped-flow methods. The formation rate constants, k_f(M^(-1).s^(-1)), for the complexation reaction, CuA + LCuAL, are as follows; X=NO_2, 8.68×10~8; X=Cl, 7.13×10~8; X=H, 6.12×10~8; X=CH_3, 5.42×10~8. The rate constants for zwitterion attack are nil within experimental error. It has been found that a linear free energy relationship exists between the stability(logK_(CuAL)^(CuA) of the complexes CuAL and log kf as follows: IogK_(CuAL)^(CuA)=0.13 + 0.83 logk_f, r=0.99. It suggested that the formation rate governed the stability of the ternary complexes. The rates of formation of the ternary complexes increased with decreasing electron-donating property of the substituents. A linear relationship was found to exist as expressed by the following equation: log(k_f^R/k_F^O) = 0.097σ, r=0.96. A mechanism involves a rapid equilibrium between CuA and L followed by a slow ring closure of L.

Determination of the acid dissociation constants of N-carboxymethyl-N-(p-hydroxy phenyl carbamoylmethyl)-2,3-dihydroxy- 5-carbomethoxy benzylamine and the stability constants of its metal complexes

The acid dissociation constants of N-carboxymethyl-N-(p-hydroxy phenyl carbamoyl- methyl)-2,3-dihydroxy-5-carbomethoxy benzylamine(CHDCB) and the stability constants of its 1:1 complexes with alkaline earth, Cd(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Fe(Ⅲ),Th(Ⅳ)and U(Ⅵ)ions have been determined at 25.0±0.1℃ and at an ionic strength of 0.1(KNO_3)by pH titration method. The probable coordination sites have also been discussed.

Dispersion characteristics of complex electromechanical parameters of porous piezoceramics

In this paper,the results of experimental study of dispersion characteristics of complex electromechanical parameters of ferroelectrically“hard”porous piezoceramics based on PZT composition were presented.Experimental samples of porous piezoceramics were fabricated using a modified method of burning-out a pore former.The complex constants of porous piezoceramics with relative porosity 16%and their frequency dependences were measured using the piezoelectric resonance analysis method.As a result of experimental studies,regions of elastic,piezoelectric and electromechanical dispersion,characterized by anomalies in the frequency dependences of the imaginary and real parts of the complex constants of porous piezoelectric ceramics were found.It was revealed also that the microstructural features of porous piezoceramics determine the character of frequency dependences of complex electromechanical parameters of porous piezoelectric ceramics.In conclu-sion,the microstructural and physical mechanisms of electromechanical losses and dispersion in porous piezoceramics were discussed.

Mechanism of phthalic acid collector in flotation separation of fluorite and rare earth

The mechanism of phthalic acid,a dicarboxylic acid collector,in flotation separation of fluorite and rare earth(RE)was studied in this paper.The experimental data of flotation show that phthalic acid,as the collector,can realize highly efficient separation of fluorite and rare earth under weakly acidic conditions.The adsorption mechanism of phthalic acid on the surface of fluorite and bastnaesite was analyzed in this paper by means of the zeta potential measurement,the Fourier transform infrared(FT-IR),the X-ray photoelectron spectroscopy(XPS)and the stability constant measurement of active metal ion and phthalic acid coo rdination complex.According to the zeta potential testing results,the surfaces of fluorite adsorb the collector phthalate ion with negative charge under weakly acidic conditions which,in turn,increases its electronegativity and results in the motion of its potential.After the reaction between phthalic acid and fluorite ores under weakly acidic conditions,the peak of the fluorite ores is found to have significant changes in the FT-IR results,indicating strong chemical adsorption on the surfaces of phthalic acid and fluorite ores.According to the XPS analysis,the peak of benzene ring of phthalic acid is as high as 2%on the surface of fluorite,while no obvious characteristic peak of benzene ring is found on the surface of bastnaesite.According to the pH potentiometric titration results,the stability constant Ktotal of calcium phthalate complex within the acid range is higher than the stability constant K’total of cerium phthalate complex,indicating that the complex generated between phthalic acid and Ca^(2+)is more stable than the complex generated between phthalic acid and Ce^(3+).The possible reason is that Ca^(2+),with the highest reticular density,plays a prevailing role in the octahedron structure of fluorite amidst the acidic media.As the active point of flotation,Ca^(2+)works with the carboxyl groups of the collector phthalic acid(-C=O-)to form polycyclic calcium phthalate complex.

Optical properties of GaAs

We have investigated the optical properties of gallium arsenide(GaAs) in the photon energy range 0.6- 6.0 eV.We obtained a refractive index which has a maximum value of 5.0 at a photon energy of 3.1 eV;an extinction coefficient which has a maximum value of 4.2 at a photon energy of 5.0 eV;the dielectric constant,the real part of the complex dielectric constant has a maximum value of 24 at a photon energy of 2.8 eV and the imaginary part of the complex dielectric constant has a maximum value of 26.0 at a photon energy of 4.8 eV;the transmittance which has a maximum value of 0.22 at a photon energy of 4.0 eV;the absorption coefficient which has a maximum value of 0.22×10~8 m^(-1) at a photon energy of 4.8 eV,the reflectance which has a maximum value of 0.68 at 5.2eV; the reflection coefficient which has a maximum value of 0.82 at a photon energy of 5.2 eV;the real part of optical conductivity has a maximum value of 14.2×10^(15) at 4.8 eV and the imaginary part of the optical conductivity has a maximum value of 6.8×10^(15) at 5.0 eV.The values obtained for the optical properties of GaAs are in good agreement with other results.

Investigation of the interaction of ethyl acetoacetate with nano alumina particle as Lewis acid in acetonitrile solvent

The enol form of ethyl acetoacetate(EAA)displays interesting spectroscopic characteristics;this form of ethyl acetylacetate is very important in condensation reaction.In this investigation,we have studied the interactions and the complex formation constants(K_(f))with nano alumina(10–20 nm)particle and alumina(mesh 135)compounds as Lewis acids in the acetonitrile solvent using absorption spectroscopy and related calculations.Furthermore,in this study we calculated the thermodynamic parameters of this reaction.The trend of reactivity of the ethyl acetoacetate(EAA)complexes toward the above Lewis acids,based on the solvent as follows:nano alumina compound>alumina compound.