Determination of stability constants by semi-integral analysis of voltammograms obtained with a computerized electrochemical system

A versatile computerized electrochemical system is used for the determination of stability constants of lead(II) propanoate and 2-hydroxypropanoate complexes by semi-integral linear sweep voltammetry. Semi-integral voltammograms are analogous in characteristics to d.c. polarograms, and the half-wave potentials (E_{$\text{1}\text{2}$}) and limiting currents (i₁) for a depolarizer can be obtained by nonlinear least-squares fitting of semi-integrally transformed voltammograms. An advantage of the proposed method is that E_{$\text{1}\text{2}$} and i₁ values are obtained from a single mercury drop (hanging or dropping mercury electrode); working time is reduced while accuracy and precision are maintained. The computer-controlled system provides automated reagent addition, signal generation, response measurement and sampling, data evaluation, etc. The results agree well with those obtained by the usual d.c. polarographie method.     

Rank annihilation factor analysis for spectrophotometric study of complex formation equilibria

The use rank annihilation factor analysis (RAFA) for spectrophotometric studies of complex formation equilibria are proposed. One-step complex formation and two successive and mononuclear complex formation systems studied successfully by proposed methods. When the complex stability constant acts as an optimizing object, and simply combined with the pure spectrum of ligand, the rank of original data matrix can be reduced by one by annihilating the information of the ligand from the original data matrix. The residual standard deviation (R.S.D.) of the residual matrix after bilinearization of the background matrix is regarded as the evaluation function. The performance of the method has been evaluated by using synthetic data. For two-step successive complex formation systems, the effects of noise level and equilibrium constants K₁ and K₂ on output of algorithm are investigated. The applicability of method for resolving the two-step successive complex formation systems with full spectral overlapping of two complex species also is shown. Spectrophotometric studies of murexide-calcium, dithiazone-nickel and methyl thymol blue (MTB)-copper are used as experimental model systems with different complexation stoichiometries and spectral overlapping of involved components.     

Adsorption effects in normal pulse polarography of adenine

Dependences of the wave height (h) of normal pulse polarograms of adenine on prepolarization potential (E_pp) were found. This effect was investigated in more detail exploiting the advantage of the A 3100 pulse polarograph after G.C. Barker in changing the pulse polarographic parameters over a wide range. From the results it was concluded that this effect is caused by the adsorption of adenine during the prepolarization. The results were compared with on principle similar results of nucleic acids.     

Die Berechnung komplexer Absorptionsgleichgewichte ionogener Substanzen in wäßrigen Lösungsmitteln mit Hilfe eines Reaktionsmodells

The solubility of ionogen substances in water and aqueous ionic solutions is important for calculation of absorption processes. Aqueous solutions with complex reaction systems behave themselves extremely nonideal. In simple cases equilibria can be determined with the concept of nonideal thermodynamics. The model used in this work is based on ideal calculation of reaction equilibria and gas solubility. The model parameters (equilibrium constants andHenry constants) for the systems SO₂-H₂O,MEA-H₂S-H₂O,DEA-H₂S-H₂O andMEA-CO₂-H₂O are computed by regression of experimental data. Equilibrium reactions are selected according toBrinkley's method. The selection of the reacting species has decisive influence on the accuracy of the data fitting. Data regression is done numerically and leads to the formulation of nonlinear systems of equations, which have to be solved for each data point. This solutions are performed in an inner loop. By using the maximum-likelihood-principle the model parameters are optimized in the superior regression loop. Experimental data for the regression are the partial pressure and the total concentration of gas in the liquid phase. The used model is able to fit these data satisfactoryly. The model parameters, which are calculated from simultaneous data regression for different temperatures, ensure a simple correlation ofvan't Hoff. However, for similar reactions equilibria in different reaction systems, it is impossible to compute the same values for the equilibrium constants.     

Computed current density in the case of slow charge-transfer coupled with a second order chemical reaction,under potentiostatic conditions (SnIV/SnII system)

Current-time curves at constant potential on plane and spherical electrode have been computed by numerical integration of the transport equations in the case of a slow charge-transfer coupled with a chemical reaction leading to a non-reactive product E₃, following the scheme:E₁+e→E₂E₁+E→E₂?E₃Results indicate that this mechanism is characterized by lower current densities than those of simple diffusion-transfer control. The current density is not proportional to depolarizer E₁ concentration. The main characteristic of these systems is that, when polarograms are analysed in terms of log k versus potential E, different straight lines are obtained depending on the concentration of the depolarizer; consequently, the apparent transfer coefficient α varies with concentration. Moreover all lines intersect at a same point lying at a potential near the equilibrium value, where the charge-transfer rate constant k is sufficiently small to be rate determining.     

Polarographic determination of stability constants and thermodynamic parameters of lead(II) propanoate and 2-hydroxypropanoate complexes with a computer-controlled system

A computer-controlled electrometric system is described. It is used for d.c. polarographic determinations of the stability constants of lead(II) propanoate and 2-hydroxypropanoate complexes at four temperatures. From the values of the monoligand complex stability constants obtained at different temperatures, standard thermodynamic functions (ΔH_j and ΔS_j) for the first and second steps of complex formation were obtained. Closed-loop interaction between the minicomputer and electrometric instrument was achieved through computer control of the potentiostat, drop-life timer, burette and valve for nitrogen purging. Computer programs are outlined for numerical and statistical evaluation of the experimental data giving E_{$\text{1}\text{2}$}i_d and slope of logarithmic presentation of polarograms, F_o functions and cumulative stability constants, β_j as well as for calculation of the standard thermodynamic functions.     

Correlation of the Extraction Constant Values of Zn2+ and Cd2+ from Phosphoric Acid Media by Bis(2,4,4-trimethylpentyl)dithiophosphinic Acid Dissolved in Toluene

Values of the extraction constants of Zn²⁺ and Cd²⁺ from aqueous phosphoric acid solutions (0.36 to 7.31 mol?L^?1) by Cyanex 301 in toluene, involving formation of the complexes ZnR₂ and CdR₂ with R being bis(2,4,4-trimethylpentyl)dithiophosphinate, have been correlated at T=298 K as a function of the ionic strength. For this purpose the activity coefficients of all of the aqueous species have been calculated taking into account both the protolytic equilibria of concentrated phosphoric acid and complexation reactions between the cations and the phosphoric acid species. Good correlations have been obtained for the extraction constant values with the ionic strength, provided the release of water molecules during the extraction processes is considered. Finally, extraction constant values are reported at infinite dilution.     

Potentiometric studies on the complexation of copper(II) by phenolic acids as discrete ligand models of humic substances

Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pK_a1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pK_a2 and pK_a3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group.     

Experimental and Theoretical Study on the Inclusion Capability of a Fluorescent Indolizine β-Cyclodextrin Sensor Towards Volatile and Semi-volatile Organic Guest

Inclusion equilibria of a new fluorescent indolizine modified β-cyclodextrin were studied in aqueous solution to evaluate its use as a fluorescent chemo-sensor for volatile organic compounds (VOCs). The host compound shows a decrease of the fluorescence intensity by adding adamantanol, benzene, toluene, phenol and p-cresol as guest. The sensing parameter (ΔI/I ₀) was used to show the sensing ability of the host. The formation constant values measured using a spectral displacement method and a specific algorithm treatment are reported. Although the guest binding ability of the sensor is not enhanced by the existence of the hydrophobic cap, this new cyclodextrin sensor shows a very strong sensing ability. The experimental values of the constants were in good agreement with the computed complexation energies, ΔE, from molecular mechanics modelling of the inclusion process.     

Multiwavelength spectrophotometric determination of acidity constants of 1-（2-thiazolylazo）-2-naphthol in methanol-water mixtures

The acid-base properties of 1-(2-thiazolylazo)-2-naphthol (TAN) in mixtures of methanol-water at 25℃and an ionic strength of 0.1 mol/L are studied by a multi-wavelength spectrophotometric method.The acidity constants of all related equilibria are estimated using the whole spectral fitting of the collected data to an established factor analysis model DATAN program was used for determination of acidity constants.The corresponding pK_a values in methanol-water mixtures were determined.There is a linear relationship between acidity constants and the mole fraction of methanol in the solvent mixtures.     

Complexation of Cd2+, Ni2+, and Ag+ metal ions with 4,13-didecyl-l,7,10,16-tetraoxa-4,13-diazacyclooctadecane in acetonitrile-ethylacetate binary mixtures

Conductometric titrations have been performed in acetonitrile-ethylacetate (AN-EtOAc) binary solutions at 288, 298, 308, and 318 K to obtain the stoichiometry, the complex stability constants and the standard thermodynamic parameters for the complexation of Cd²⁺, Ni²⁺, and Ag⁺ cations with 4,13-didecyl-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (cryptand 22DD). The stability constants of the resulting 1: 1 complexes formed between the metal cations and the ligand were determined by computer fitting of the conductance-mole ratio data. There is a non-linear relationship between the logK _f values of complexes and the mole fraction of ethylacetate in the mixed solvent system. In addition, the conductometric data show that the stoichiometry of the complexes formed between the Cd²⁺, Ni²⁺, and Ag⁺ cations with the ligand changes with the nature of the solvent. The standard enthalpy and entropy values for the 1: 1 [ML] complexation reactions were evaluated from the temperature dependence of the formation constants. Thermodynamically, the complexation processes of the metal cations with the C22DD, is mainly entropy governed and the values of thermodynamic parameters are influenced by the nature and composition of the binary mixed solvent solutions.     

Enantiomeric separation of racemic clenbuterol by capillary zone electrophoresis

A method for capillary electrophoretic enantiomeric separation of a racemic clenbuterol has been established with hydroxypropyl-β-cyclodextrin as the chiral selector. General equations and data analysis are presented to relate mobility to the equilibrium constants in simple binding equilibria and used to determine binding constants and thermodynamic parameters for host-guest complexation of clenbuterol enantiomers with hydroxypropyl-β-cyclodextrin as a selector. The effects of β-cyclodextrin type and concentration, buffer type, concentration and pH, as well as separation voltage and capillary temperature were investigated in detail. A maximal resolution of 6.78 was obtained. The binding constants of the host-guest complex of clenbuterol enantiomers with hydroxypropyl-β-cyclodextrin, K _R-CD and K _S-CD are 22.50 and 43.09 l mol^-1, respectively.     

Potentiometric Studies on the Equilibria of Flufenamic Acid in Aqueous Solutions and in Two-phase Organic Solvent + Water Systems

In this paper, the flufenamic acid equilibria in aqueous solution and in two-phase organic solvent + aqueous solution are described and presented. The dissociation constants K _a1 and K _a2 were determined in MDM + water mixtures. The Yashuda-Shedlovsky extrapolation procedure has been used to obtain the values of K _a1 and K _a2 in aqueous solutions. The distribution ratio D was measured in the toluene + water system over a wide range of pH by the shaking flask method. Based on the results of potentiometric titrations in two-phase organic solvent (benzene, ethylbenzene, toluene, carbon tetrachloride, chloroform, chlorobenzene, and bromobenzene) + aqueous systems, and using models of single and multistep equilibria, the values of distribution constants K _D and dimerization constants K _dim were calculated. The influences of polarity of the applied solvents and pH of the aqueous phase, on the speciation of the particular forms of flufenamic acid in both phases, were demonstrated.     

Proton NMR probing of stoichiometry and thermodynamic data for the complexation of Na and Li ions with 15-Crown-5 in acetonitrile-nitrobenzene mixtures

Proton NMR was used to study the complexation reaction of Li⁺ and Na⁺ ions with 15-Crown-5 (15C5) in a number of binary acetonitrile (AN)-nitrobenzene (NB) mixtures at different temperatures. In all cases, the exchange between free and complexed 15C5 was fast on the NMR timescale and only a single population average ¹H signal was observed. The formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift mole ratio data. There is an inverse relationship between the complex stability and the amount of AN in the solvent mixtures. The enthalpy and entropy values for the complexation reaction were evaluated from the temperature dependence of the formation constants. In all the solvent mixtures studied, the resulting complex is enthalpy stabilized but entropy destabilized. Finally, the experimental results were compared with theoretical ones that were obtained from molecular modeling methods. Based on our results, it is most probable that Li⁺-15C5 in solvent stays in a rather nesting complex form with greater LogK_f values, but Na⁺-15C5 forms a complete perching complex form with lower LogK_f values.     

Resolving of Voltammetric Data for the Ni–Glycine and Cu–Glycine Complexation Systems with Reversible and Irreversible Electrochemical Response Using MCR-ALS

The Ni?Cglycine and Cu?Cglycine systems, which form successive complexes, were studied by differential pulse polarography. The Ni?Cglycine complexes were inert while the Cu?Cglycine system showed labile behavior. An irreversible electrochemical response was found for the Cu?Cglycine system. The data were analyzed both by conventional methods (hard modeling) and the multivariate curve resolution method with alternating least-squares optimization (MCR-ALS, soft modeling approach). Resolving titration data for Cu²⁺ and Ni²⁺ with glycine as the complexing ligand shows that this method is a powerful tool for the determination of stability constants of metal complexes, especially when the conventional methods involve complicated and time consuming approaches such as for systems with an irreversible reduction process. Although for labile complexes the current is not always linear with respect to the concentrations, the results obtained by the two approaches are similar, so the variation from linearity of the signals is small and can be neglected. Also, the analysis of the labile complex data by a Gaussian peak adjustment (GPA) algorithm showed that this system has a small deviation from bilinearity. Thus, the MCR method provided good estimations of the complexation parameters, and is suitable for use as a complementary tool for studying systems with successive labile or inert complexes with both reversible and irreversible responses. Differential pulse polarograms were measured at room temperature for buffer solutions with pH = 7.5 and 0.1?mol?L^?1 ionic strength.     

Thermodynamic study of complex formation between Ni2+ and Co2+ cations and 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix 5) in binary mixed nonaqueous solutions

Conductometric titrations were performed in pure and binary solvent solutions of ethyl acetate (EtOAc), methyl acetate (MeOAc) and methanol (MeOH) with acetonitrile (AN) at 288, 298, 308, and 318 K to determine the stoichiometry, the complex stability constants and the standard thermodynamic parameters for the complexation of nickel(II) and cobalt(II) cations with 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix 5). The stability constants of the resulting 1:1 complexes formed between the metal cations and the ligand in different solvent mixtures were determined by computer fitting of the conductance-mole ratio data. The results revealed that the stability order of (kryptofix 5)-Ni²⁺ and (kryptofix 5)-Co²⁺ complexes changes with nature and composition of the solvent system. There is a non-linear relationship between the logK _f values of complexes and the mole fraction of acetonitrile in the mixed solvent system. In addition, the conductometric data show that the stoichiometry of the complexes formed between the nickel(II) and cobalt(II) cations with the acyclic ligand changes with the nature of the solvent. The enthalpy and entropy values for the 1: 1 [ML] complexation reactions were evaluated from the temperature dependence of the formation constants. Thermodynamically, in most of systems, the complexation processes of nickel(II) and cobalt(II) cations with kryptofix 5, are both enthalpy and entropy stabilized and the values of these parameters are influenced by the nature and composition of the binary mixed solvent solutions.     

Study of the complexing equilibria involved between zirconium and gallion and 4-(2-pyridylazo) resorcinol in aqueous solution

Zirconium forms two complexes each with Gallion, 1:1 in 0.1 M HCl (λ_max 600 nm) and 2:1 (Zr:Gallion) at pH 2.0 (λ_max 540 nm) and with, PAR, 1:2 (Zr:PAR) in 0.1 M HCl (λ_max 410 nm) and 1:1 at pH 2.0 (λ_max 420 nm). In all cases the exact nature of the equilibrium involved with the hydroxy species of zirconium participating in complexation reaction is evaluated. Kinetic study, and the number of protons liberated during complexation reaction have been studied and the position of the chelate rings have been suggested. The values of equilibrium constants for these complexes have also been evaluated.     

Intermediates in asymmetric hydrogenation : The structure and 31P NMR spectra of rhodium enamide complexes containing 1R, 2R-trans-1,2-bis (diphenylphosphinomethyl) cyclo buta

Hydrogenation of bicyclo[2.2.1]heptadiene-1R,2R-(trans-1,2-bis(diphenylphosphinomethyl)cyclbutane rhodium (I) tetrafluoroborate in methanol gives a solvent adduct which reacts with N-acyldehydroamino acids and their esters to give air-unstable scarlet to yellow complexes. Effects of structure variation in the enamide on the ³¹P NMR spectra of these species are reported and discussed with reference to (a) the equilibrium between methanol and enamide complexes; (b) the ratio of diastereomeric enamide complexes formed; (c) the temperature dependence of this ratio; (d) the rate of complexation equilibria and (e) the structure of enamide complexes, which are normally bidentate with binding via the olefin and amide groups. In certain cases the complex may be terdentate and E-enamides bind through the olefin and carboxyl groups. Each mode of binding gives rise to characteristic ³¹P NMR spectra with regard to P-P and P-Rh coupling constants.     

Reverse pulse voltammetry in ec2 reactions: Electrochemistry of 1-alkyl-4-t-butylpyridinium ions

The applications of the reverse pulse method are extended in order to distinguish between different paths of electrodimerization. The method for determination of rate constants of the chemical reaction coupled with charge transfer (ec₂) is further developed. Measurements of K′_d vs. t_p provide valuable information for the determination of rate constants.The reverse pulse method is applied in the study of the electrodimerization of 1-alkyl-4-t-butylpyridinium ions (1-alkyl=?CH₃; ?CH₂CH₃; ?CH(CH ₃)₂) in acetonitrile. It is found that the electrodimerization mechanism is consistent with the sequence: Py⁺ + e = Py ? $\text{1}\text{2}$ Py₂. The formal potential E^o′ is measured directly for 1-CH(CH₃)₂, and indirectly for the other pyridium ions. All values are identical within experimental error (E^o′ = ?1.835 V vs. Ag/Ag⁺).The values of k_d and k_m are measured. With an increase in the size of the l-alkyl group, k_d decreases and k_m increases. This is consistent with the expected “stabilization” of the radicals due to the increase of the l-alkyl group size which hinders the dimerization site (2- and 6-positions).     

Electrochemical Behaviour Study of Mixed Ligand Complexes of Diaminopropane and Phthalate with Cd(II) Using Differential Pulse Polarography and Cyclic Voltammetry Techniques

Abstract

Differential pulse(d. p.)polarography has been used to study the simple and mixed ligand complexes of 1, 3 diaminopropane (DAMP) and phthalate(PHLT) with Cd(II) at constant ionic strength (u= 1.0 M NaNO₃) at 25°C The overall formation constants of simple and mixed complexes were calculated. The reduction of the simple and mixed species is reversible and diffusion controlled. The postive values of the mixing constants for the mixed-ligand complexes indicate that the mixed-ligand complexes are more stable than simple binary complexes. The equilibria between the various mixed-ligand species in the solution and their equilibrium are given.