The thermodynamic characteristics of complex formation between Cd<Superscript>2+</Superscript> and ethylenediamine-N,N′-disuccinic acid in aqueous solution

The enthalpies of complex formation between ethylenediamine-N,N′-disuccinic acid (H₄A) and Cd²⁺ ions were determined calorimetrically at 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 (KNO₃). The thermodynamic characteristics of formation of the CdA^2? and CdHA^? complexes at fixed and zero ionic strengths were calculated. The values obtained were interpreted.     

Experimental Determination of the Isotherm at 15°C of the System Mg<Superscript>2+</Superscript>/Cl<Superscript>−</Superscript>, SO<Subscript>4</Subscript><Superscript>2</Superscript>–H<Subscript>2</Subscript>O

Summary.  The diagram of the ternary system Mg²⁺/Cl⁻, SO₄ ²⁻–H₂O was established at 15°C by means of analytical and conductimetric measurements. Three compounds were found in this diagram, which are MgSO₄·6H₂O, MgSO₄·7H₂O, and MgCl₂·6H₂O. The solubility field of MgSO₄·7H₂O is important whereas those of MgSO₄·6H₂O and MgCl₂·6H₂O are small. The compositions (mass-%) of the two invariant points determined by the two methods are: MgSO₄:MgCl₂=2.73:33.80 and MgSO₄: MgCl₂=3.38:28.91. Both the measured and the calculated isotherm at 15°C have been used for modelling of the diagram Mg²⁺/Cl⁻, SO₄ ²⁻–H₂O between 0 and 35°C. The polythermal invariant point was approximately located between 15 and 10°C.  Corresponding author. E-mail: ariguib@planet.tn Received October 16, 2002; accepted (revised) December 3, 2002 Published online April 24, 2003 RID="a" ID="a" Dedicated to Prof. Dr. Heinz Gamsj?ger on the occasion of his 70^th birthday     

Thermodynamics of the complex formation between Cu<Superscript>2+</Superscript> and triglycine in water–ethanol solutions at 298 K

Thermodynamic functions Δ_r H, Δ_r G, and TΔ_r S of the complex formation between Cu²⁺ and triglycine in water–ethanol solutions are calculated on the basis of calorimetric data. It is found that raising the concentration of EtOH results in a monotonic increase in the exothermic effect of [CuHL]²⁺ complex formation due to the weakening of triglycine solvation with the mutual compensation of ion solvation contributions. The enthalpy of [CuL]⁺ complex formation has an exothermic maximum at 0.1?0.3 molar fractions of EtOH due to competition between the solvation contributions from ions and ligands.     

Complexation of 4′-nitrobenzo-15-crown-5 with Mg<Superscript>2+</Superscript>, Ca<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript> and Ba<Superscript>2+</Superscript> metal cations in acetonitrile-methanol binary solutions

The complex formation reactions between Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ metal cations with macrocyclic ligand, 4′-nitrobenzo-15C5, were studied in acetonitrile (AN)-methanol (MeOH) binary mixtures at different temperatures using conductometric method. The results show that 4′-nitrobenzo-15C5 forms 1:1 [ML] complexes with Mg²⁺, Ca²⁺ and Sr²⁺ metal cations in solutions. But in the case of Ba²⁺ cation a 1:2 [ML₂] complex is formed in these solvent systems. The stability of the complexes is sensitive to the solvent composition and a non-linear behavior was observed for variation of logK _f of the complexes versus the composition of the binary mixed solvents. The stability constants of complexes decrease suddenly with increasing the concentration of methanol in this binary system. The values of thermodynamic parameters (ΔH _c^° and ΔS _c^°) for formation of (4′-nitrobenzo-15C5.Mg)²⁺, (4′-nitrobenzo-15C5.Ca)²⁺ and (4′-nitrobenzo-15C5.Sr)²⁺ complexes were obtained from temperature dependence of the stability constants and the results show that these parameters are affected by the nature and composition of the mixed solvents. A non-linear behavior is observed between the ΔS _c^° and the composition of the mixed solvents.     

A thermodynamic study of complexation process between <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-dipyridoxylidene(1,4-butanediamine) and Cd<Superscript>2+</Superscript> in some binary mixed solvents using conductometry

Complexation of the Cd²⁺ ion with N,N′-dipyridoxylidene(1,4-butanediamine) Schiff base was studied in pure solvents including acetonitrile (AN), ethanol (EtOH), methanol (MeOH), tetrahydrofuran (THF), dimethylformamide (DMF), water (H₂O), and various binary solvent mixtures of acetonitrile–ethanol (AN–EtOH), acetonitrile–methanol (AN–MeOH), acetonitrile–tetrahydrofuran (AN–THF), acetonitrile–dimethylformamide (AN–DMF), and acetonitrile–water (AN–H₂O) systems at different temperatures using the conductometric method. The conductance data show that the stoichiometry of complex is 1: 1 [ML] in all solvent systems. A non-linear behavior was observed for changes of log K_f of [Cd(N,N′-dipyridoxylidene(1,4-butanediamine)] complex versus the composition of the binary mixed solvents, which was explained in terms of solvent–solvent interactions. The results show that the thermodynamics of complexation reaction is affected by the nature and composition of the mixed solvents.     

Comparison of sorption of Pb<Superscript>2+</Superscript> and Cd<Superscript>2+</Superscript> on Kaolinite clay and polyvinyl alcohol-modified Kaolinite clay

Kaolinite clay obtained from Ubulu-Ukwu, Delta state in Nigeria was modified with polyvinyl alcohol (PVA) reagent to obtain PVA-modified Kaolinite clay adsorbent. Scanning Electron Microscopy (SEM) of the PVA-modified adsorbent suggests that Kaolinite clay particles were made more compact in nature with no definite structure. Modification of Kaolinite clay with PVA increased its adsorption capacity for 300 mg/L Pb²⁺ and Cd²⁺ by a factor of at least 6, i.e., from 4.5 mg/g to 36.23 mg/g and from 4.38 mg/g to 29.85 mg/g, respectively, at 298 K. Binary mixtures of Pb²⁺ and Cd²⁺ decreased the adsorption capacity of Unmodified Kaolinite clay for Pb²⁺ by 26.3% and for Cd²⁺ by 0.07%, respectively. In contrast, for PVA-modified Kaolinite clay, the reductions were up to 50.9% and 58.5% for Pb²⁺ and Cd²⁺, respectively. The adsorption data of Pb²⁺ and Cd²⁺ onto both Unmodified and PVA-modified Kaolinite clay adsorbents were found to fit the Pseudo-Second Order Kinetic model (PSOM), indicating that adsorption on both surfaces was mainly by chemisorption and is concentration dependent. However, kinetic adsorption data from both adsorbent generally failed the Pseudo-First order Kinetic model (PFOM) test. Extents of desorption of 91% Pb²⁺ and 94% Cd²⁺ were obtained, using 0.1 M HCl, for the Unmodified Kaolinite clay adsorbent. It was found that 99% Pb²⁺ and 97% Cd²⁺, were desorbed, for PVA-modified Kaolinite clay adsorbents within 3 min for 60 mg/L of the metal ions adsorbed by the adsorbents.     

Isothermal solubility diagram of the 2Na<Superscript>+</Superscript>,Mg<Superscript>2+</Superscript>‖2Cl<Superscript>−</Superscript>, 2ClO<Stack><Subscript>3</Subscript><Superscript>‒</Superscript></Stack>-H<Subscript>2</Subscript>O quaternary system at 20 and 100°C

The solubility in the 2Na⁺,Mg²⁺‖2Cl⁻, 2ClO₃⁻-H₂O system was studied at 20 and 100°C and the solubility diagrams were plotted. New compounds were not found to form in the title quaternary reciprocal system. The sodium chloride field was observed to expand with rising temperature.     

Studies on structure and electrochemical properties of pillared M–MnO<Subscript>2</Subscript> (M=Ba<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript>, ZrO<Superscript>2+</Superscript>)

Supramolecular pillared oxides were prepared through the intercalation of M²⁺ cations into a MnO₂ host matrix by the method of ion exchange between the precursor δ-K _x MnO₂ and the corresponding guest. The materials M-MnO₂ crystallize in the hexagonal system, the same structure as the precursor, with a larger interlamellar spacing. In the case of ZrO-MnO₂, extended X-ray absorption fine structure (EXAFS) determination indicates that the Zr atom locates between the MnO₂ layers forming a stable structure. Compared with the precursor, the cycling property of M-MnO₂ was improved distinctly, while the capacity decreased to some degree due to the strong interaction between pillars and the host matrix. Among these pillared materials, ZrO-MnO₂ has an advanced reversible capacity of 161.5 mAh·g⁻¹ and improved cycling behavior compared with the precursor.     

Thermodynamics of the formation of Cu<Superscript>2+</Superscript>–glycyl-glycyl-glycine complex in water–ethanol solutions at 298 K

The stability constants of monoligand complexes of copper(II) ions with glycyl-glycyl-glycine zwitterions (triglycine, HL^±) and triglycinate ions (L^?) in a water–ethanol solvent with 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol at an ionic strength of 0.1 created by sodium perchlorate and temperature Т = 298.15 K are determined by means of potentiometric titration. It is found that an increase of ethanol content improves the stability of the investigated complexes, due mainly to the resolvation of ligands.     

Complexation of 4′-Nitrobenzo-15-crown-5 with Zn<Superscript>2+</Superscript>, Mn<Superscript>2+</Superscript>, Cr<Superscript>3+</Superscript> and Sn<Superscript>4+</Superscript> Cations in Acetonitrile–Ethanol Binary Mixtures

The complexation reactions of 4′-nitrobenzo-15-crown-5 (4′NB15C5) with Zn²⁺, Mn²⁺, Cr³⁺ and Sn⁴⁺ cations were studied in acetonitrile–ethanol (AN–EtOH) binary solvent mixtures at different temperatures by the electrical conductometry method. The stability constants of the resulting 1:1 complexes were determined from computer fitting of the conductance versus mole ratio data. The results show that the selectivity order of 4′NB15C5 for the metal cations in the AN–EtOH (mol-%AN=76) binary solvent at 298.15 K is: Cr³⁺>Mn²⁺≈Zn²⁺>Sn⁴⁺, but the selectivity order changes with the composition of the mixed solvents. A nonlinear relationship was observed between the stability constants (log ₁₀ K _f) of these complexes and the composition of the AN–EtOH binary solvents. The corresponding thermodynamic parameters (DH_c^o, DS_c^o)(\Delta H_{\mathrm{c}}^{\mathrm{o}}, \Delta S_{\mathrm{c}}^{\mathrm{o}}) were obtained from the temperature dependence of the stability constants using van’t Hoff plots. The results show that the values and also the sign of these parameters are influenced by the nature and composition of the mixed solvents.     

Stability of coordination compounds of Ni<Superscript>2+</Superscript> and Co<Superscript>2+</Superscript> ions with succinic acid anion in water–ethanol solvents

Stability constants of the coordination compounds of nickel(II) and cobalt(II) ions with succinic acid anion in water–ethanol solvents are determined via potentiometric titration at ionic strength of 0.1 and at T = 298.15 K. It is found that logβ values of monoligand complexes of these ions and succinic acid anions rise along with the content of ethanol in solution (X _EtOH = 0–0.7 mole fractions). Based on an analysis of the thermodynamic characteristics of the solvation of the reagents involved in complex formation, it is found that the increased stability of succinate complexes of nickel(II) and cobalt(II) ions in water–ethanol solvents is mainly determined by the weakening of the solvation of succinic acid anion (Y^2?).     

Research on photosensitivity of benzoquinones and benzoquinoneimines in the sunlight/Fe<Superscript>2+</Superscript>/S<Subscript>2</Subscript>O<Subscript>8</Subscript><Superscript>2−</Superscript> system

This paper investigated the photodegradation characteristics of benzoquinones and benzoquinoneimines. The photosensitivity of benzoquinones and benzoquinoneimines were analyzed by measuring the yield of SO ₄ ^?· in a light/Fe²⁺/S₂O₈ ^2? system and the degradation mechanism of benzoquinones, then discussed benzoquinoneimines in light/Fe²⁺/S₂O₈ ^2? and light/S₂O₈ ^2? system. The results revealed that a more aggressive oxidation of benzoquinones and benzoquinoneimines by the sunlight/Fe²⁺/S₂O₈ ^2? method showed a more rapid and more complete removal of chromaticity than that of the UV/Fe²⁺/S₂O₈ ^2? method. It was showed that they were photosensitizers, and they could generate ¹O₂ and O ₂ ^?· which could promote the formation of SO ₄ ^?· and ^·OH in the sunlight system. Nevertheless, for benzoquinones, the sunlight/S₂O₈ ^2? method was superior to the UV/S₂O₈ ^2? method. For benzoquinoneimines, the sunlight/S₂O₈ ^2? method was inferior to the UV/S₂O₈ ^2? method. In addition, the yield of SO ₄ ^?· in the sunlight/Fe²⁺/S₂O₈ ^2? system was more than that of the UV/Fe²⁺/S₂O₈ ^2? system. Therefore, the photosensitivity of benzoquinones is superior to benzoquinoneimines in water treatment.     

Framework coordination polymer based on the [Re<Subscript>3</Subscript>Mo<Subscript>3</Subscript>S<Subscript>8</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>6–</Superscript>heterometallic cluster anions and Cd<Superscript>2+</Superscript> cations

A new coordination polymer, [Cd(NH₃)₄]₂{Cd[Re₃Mo₃S₈(CN)₆]}·1.5H₂O (I), was prepared by the reaction between solutions of Cd(CH₃COO)₂ · 2H₂O in aqueous ammonia and CaK₄[Re₃Mo₃S₈(CN)₆] · 8H₂O in water. The crystals are cubic, space group Fm3m (Prussian blue structural type); a = 15.0268(4) Å (CIF file CSD no. 431555). According to ESR data, compound I is paramagnetic, g-factor is 2.298. Thermal stability investigation by TGA and powder X-ray diffraction showed that elimination of coordinated NH₃ molecules is accompanied by sample amorphization.     

Cross-sections for formation of <Superscript>178m2</Superscript>Hf and <Superscript>179m2</Superscript>Hf through reactions on natural hafnium at neutron energy 14.8 ± 0.2 MeV

The cross sections for formation of metastable state of ¹⁷⁸Hf (^178m2Hf, 574.215 keV, 31 y) and ¹⁷⁹Hf (^179m2Hf, 362.55 keV, 25.05 d) through reactions induced by 14.8 ± 0.2 MeV neutrons on natural hafnium were measured for the first time. The monoenergetic neutron beam was produced via the ³H(d, n)⁴He reaction on ZF-300-II Intense Neutron Generator at Lanzhou University. Induced gamma activities were measured by a gamma-ray spectrometer with high-purity germanium (HPGe) detector. Measurements were corrected for gamma-ray attenuations, random coincidence (pile-up), dead time and fluctuation of neutron flux. The neutron fluence were determined by the cross section of ⁹³Nb(n, 2n)^92mNb reaction. The neutron energy in the measurement were by the cross section ratios of ⁹⁰Zr(n, 2n)^89m+gZr and ⁹³Nb(n, 2n)^92mNb reactions.     

Standard thermodynamic functions and constants of the formation of Nd<Superscript>3+</Superscript> and Lа<Superscript>3+</Superscript> complexes with glycine in aqueous solutions at 298 K

The enthalpies of complexation of glycine (HGly^±) with Nd³⁺ and La³⁺ ions at 298.15 K and at an ionic strength of 0.5 (KNO3) are determined by means of calorimetry. The thermodynamic characteristics of the reactions of formation are calculated for NdGly²⁺, NdGly ₂ ⁺ , LaGly²⁺, and LaGly ₂ ⁺ complexes.     

Synthesis and crystal structure of a cyanide-bridged one-dimensional nickel(II) complex with alternating [Ni(En)<Superscript>2</Superscript>]<Superscript>2+</Superscript> and [Ni(CN)<Subscript>4</Subscript>]<Superscript>2−</Superscript> ions

The complex [Ni(En)₂][Ni(CN)₄] · 3.5H₂O (I) (En = ethylenediamine) was synthesized by the reaction of [Ni(En)₂](ClO₄)₂ and K₂[Ni(CN)₄] in an H-shaped tube. The crystal structure of I has been determined by single-crystal X-ray analysis. The crystal of complex I is orthorhombic, space group Pnna with a = 28.151(3), b = 8.3946(8), c = 14.5441(13)Å, M =404.76, Z = 8, V = 3437.0(5)ų. The structure of complex I reveals infinite zigzag chains shaped structure are formed by cis-Ni(En)₂-μ-(NC)₂, cis-μ-(NC)₂Ni(CN)₂, and trans-μ-(CN)₂Ni(En)₂.     

Study on nonlinear kinetic and thermodynamics of oscillating reaction of amino Acid-BrO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack>-Mn<Superscript>2+</Superscript>-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-acetone system

With the help of the kinetic parameters (the rate constant (k _in k _p) and the apparent activation energy (E _in E _p) of the oscillatory induction period and oscillation period) of the oscillating reaction using thirteen amino acids, leucine (Leu), threonine (Thr), arginine (Arg), lysine (Lys), histidine (His), alanine (Ala), glutamine (Glu), glycine (Gly), methionine (Met), cystine (Cys), tryptophan (Trp), serine (Ser) and tyrosine (Tyr), as organic substrates in amino acid-BrO₃⁻-Mn²⁺-H₂SO₄-acetone system, then based on the Oregonator model and the thermodynamics theory on irreversible process, the thermodynamic function (ΔH _in, ΔG _in, ΔS _in and ΔH _p, ΔG _p, ΔS _p) of these oscillating system are studied. The results indicate the entropy ΔS of these oscillating reaction are negative, thereby it is proved that the oscillating reaction is a noequilibrium system with dissipation structure in agreement with the character of the oscillating reaction from disorder to order in irreversible thermodynamics. These are satisfactorily to explain the experimental phenomena.     

Interaction between oxygen and polycrystalline palladium at O<Subscript>2</Subscript> pressures of 10<Superscript>−6</Superscript>–10 Pa

The interaction between oxygen and polycrystalline palladium (Pd(poly)) at \(P_{O_2 } \) = 2.6 × 10^?6–10 Pa and T = 300–1300 K was studied by the thermal desorption (TD) method. The interaction between O₂ and Pd(poly) is governed by the O₂ pressure and the sample temperature. At low pressures of \(P_{O_2 } \) (≤1.3 × 10^?5 Pa), O₂ is chemisorbed dissociatively on the Pd(poly) surface. During chemisorption, the O_ads-surface bond energy and the O₂ sticking coefficient gradually decrease as the surface coverage θ increases. At \(P_{O_2 } \) ≥ 10^?2 Pa and T ≤ 500 K, after the saturation of the O_ads layer (θ ～ 0.5), O_ads atoms penetrate under the surface layer of the metal to form surface palladium oxide. At \(P_{O_2 } \) ≥ 1 Pa and T > 500 K, after the saturation of the surface oxide film 2 ML in thickness (n ～ 2), O_ads atoms penetrate into the oxide film and then into the subsurface palladium layer and diffuse deep into the metal bulk. As a result, the oxygen uptake at 700 K is n ～ 50. Upon heating, the surface oxides decompose, desorbing O₂, which gives rise to a low-temperature TD peak with T _max = 715 K. The release of oxygen inserted in the subsurface layers of palladium shows itself as a distinct high-temperature TD peak with T _max ≥ 750 K.     

Molecular Interactions in Propylene Carbonate + <Emphasis Type="Italic">n</Emphasis>-Alkanols at 25 <Superscript>∘</Superscript>C

Densities and viscosities of the binary mixtures of propylene carbonate with methanol, ethanol, propanol, butanol, and hexanol, along with those of the pure liquids, were measured over the entire mole fraction range at 25 C. Using the experimental values of densities and viscosities , the excess molar volumes V^E, viscosity deviations , excess Gibbs energies of activation of viscous flow G^E, and Grunberg–Nissan interaction parameters d₁₂ were calculated from the linear dependence of these parameters on the composition of the mixtures.