Formation of Cu(II)—dicyandiamide complexes in neutral and acidic aqueous solutions

This work presents spectroscopic studies and electrochemical characterization of Cu(II)—dicyandiamide (DCDA) complex formation. The range of conditions leading to the precipitation of the complex is significantly larger than that presented in the literature. In all cases the stoichiometry of the compound is: [Cu(DCDA)₂(SO₄)(H₂O)₅). The spectroscopic data suggest that DCDA is a monodentate ligand forming a bond with Cu²⁺ via the nitryl nitrogen. Electroreduction of this complex is a two-step process occurring through a Cu(I)—DCDA intermediate.     

Investigations into the formation and characterization of microemulsions. I. Phase diagrams of the ternary system water—sodium alkyl benzene sulfonate—hexanol and the quaternary system water—xylene—sodium alkyl benzene sulfonate—hexanol

The phase diagrams of the ternary system water—sodium alkylbenzene sulfonate (NaDBS)-hexanol and the quaternary system water—xylene—NADBS—hexanol have been established at three different temperatures, namely 25, 37, and 50°C. The different phases formed have been qualitatively examined using optical (phase contrast and polarizing) microscopy. The textures of the various liquid crystalline phases in the ternary system have been identified, by comparison with previous studies in the literature. Some of the liquid crystalline phases have been quantitatively assessed using low angle X-ray diffraction. The latter measurements were also used to determine the unit cell dimensions in the various phases studied. With the quaternary system, particular attention was paid to the transparent region which consisted of an L₂ (inverse micellar) phase extending into another transparent region which has a blue “tinge” in some cases, namely the microemulsion (M) region. The amount of water solubilized in the L₂ (reverse micelle) or M + L₂ phase was calculated from the phase diagrams. With the ternary system the results showed a maximum in moles of water solubilized per mole total surfactant (NaDBS + hexanol) at a concentration of 0.3 mole surfactant, at an optimum molar ratio of n-hexanol to NaDBS of 4.5:1. This maximum was about twice with the quaternary system, when compared with that of the ternary system, indicating the importance of the role of xylene in solubilization of water by the surfactants. The present investigation has also shown that the extent of the microemulsion region is significantly reduced by increases of temperature when the NaDBS is lower than 15 wt%.     

The solubility of uranium(IV) hydrous oxide in sodium hydroxide solutions under reducing conditions

The solubility of hydrous UO₂ in sodium hydroxide solutions containing sodium dithionite and/or Zn metal powder as reductants has been measured. The results provide no firm evidence for any amphoteric behavior of U(IV) but do set an upper limit of K ≤ 2 x 10^?23 for the hypothetical reaction:

The results provide no evidence for such a reaction.     

17O and 183W NMR studies of the paratungstate anions in aqueous solutions

¹⁷O (40.7 MHz) and ¹⁸³W (12.5 MHz) NMR spectra of aqueous Na₁₀[H₂W₁₂O₄₂]·27H₂O (1), Na₆[W₇O₂₄]·14H₂O (2) and (NH₄)₆[Mo₇O₂₄]·nH₂O solutions, as well as of 2, 1 and 0.1 M Na₂WO₄ and 2 M Li₂WO₄ solutions acidified up to P = 0.5, 1 and 1.14 have been measured. The composition of the W₇O₂₄^6? anion remains unchanged (2), its structure being similar to that of Mo₇O₂₄^6?183W NMR spectrum shows three resonances with the chemical shifts + 269.2, ?98.8 and ?178.9 ppm relative to WO₄^2? and intensity ratio 1:4:2. “Paratungstate A” produced during polycondensation of WO₄^2? at P ? 1.17 is identical with heptatungstate W₇O₂₄^6?. The [H₂W₁₂O₄₂]^10?183W NMR spectrum in the acidified 2 M Li₂WO₄ solution has four resonances with the chemical shifts in the range - 105–145 ppm and intensity ratio 1:2:1:2. As suggested by NMR data, the H₂W₁₂O₄₂^10? ? W₇O₂₄^6? transformations occur, which depend upon concentration and temperature.     

Effect of added salts on the rates of dissociation and racemization of tris(1,10-phenanthroline)iron(II) ion in aqueous methanol solutions

The kinetics of dissociation and racemization of [Fe(phen)₃]²⁺ have been studied in aqueous methanol solutions containing perchlorate, chloride, and thiocyanate ions. The racemization rate was decreased by ClO^?₄ and increased by SCN^?, while the dissociation rate was decreased by ClO^?₄ and increased slightly by Cl^? and remarkably by SCN^?. The effect of anions on the reaction rates became remarkable with the increase in methanol content of the solutions. The results were reasonably explained in terms of ion association. The dissociation rate of the complex ion in the ion-pair increased in the order, ClO^?₄ < Cl^? < SCN^?, of associated anions, suggesting the ion-pair interchange mechanism for the dissociation. The ion-association constants were determined to be 11 ± 4, 18 ± 4, and 25 ± 15 (I = 0.1, 25°C) for ClO^?₄, Cl^?, and SCN^?, respectively, in 0.64 mole-fraction (0.8 volume-fraction) aqueous methanol.     

The reaction of pentaborane(9) with sodium cyanide and sodium cyanotrihydroborate

The reaction of pentaborane(9) with NaCN occurs in a 1:1 molar ratio at temperatures between ? 30° and + 10°C to yield the complex Na[B₅H₉CN], which can be isolated in the form of a dioxanate. When excess pentaborane(9) is used the reaction is relatively clean and yields predominantly the [B₉H₁₄]^? ion. With NaBH ₃CN no intermediates of the type Na[B₅H₉CN] are detected, and the major product is the [B₉H₁₄]^? ion, but no hydrogen is evolved in the reaction. Structures for the intermediate anions are suggested. No monocarbon carbaboranes were detected in any of the reactions.     

Kinetic studies of solvent extraction of metal complexes—IX. Rate of complex formation of chromium(III) with acetylacetone in aqueous perchlorate solutions and in two polar organic solvents

The rate of complex formation of chromium(III) with acetylacetone in aqueous perchlorate solutions was determined by a solvent extraction method in 4-methyl-2-pentanone and 4-methyl-2-pentanol. The rate of complex formation in the organic solvents was also studied by a spectrophotometric method. On the basis of the results that the rate of complex formation was nearly the same in these three media, a mechanism for the extraction of the metal ions in aqueous perchlorate solutions with acetylacetone into these polar organic solvents was proposed.     

On the tri-n-octylammonium chlorocomplexes of Sn(IV) in benzene solution

Extracts with tri-n-octylammonium chlorocomplexes of Sn(IV) of various compositions, included the N-deuterated compounds, were prepared and investigated by IR spectroscopy and conductivity measurements. Three Sn(IV) complexes were found: (TOAH⁺)₂SnCl₆^2? (2:1-complex), TOAH⁺SnCl₅^? (1:1-complex) and a complex with the stoichiometric ratio TOA:Sn(IV) > 2. The cation of the latter contains the groups (TOAH…Cl…HTOA)⁺ and TOAH⁺ and that species is supposed to be a 3:1-complex (TOAH…Cl…HTOA)⁺TOAH⁺SnCl₆^2?.     

On the tri-n-octylammonium chlorocomplexes of Sn(II) in benzene solution

Loading experiments in the extraction system TOAH⁺Cl^?/benzene-SnCl₂-HCl and measurements of the IR spectra and the specific conductivities κ of the extracts revealed the occurrence of two Sn(II)complexes: TOAH⁺SnCl₃ (1:1-complex) and (TOAH…Cl…HTOA)⁺SnC1₃^? (2:1-complex). The shift of the νNH frequencies of these complexes with N-deuteration, expressed by the ratio νHN/νND, amounts to 1.33 and 1.28 respectively. This agrees very well with corresponding values of complexes with analogous or similar composition.     

Copper(II) complexes of diaminodiamides in aqueous solution

The basicity constants of N,N′-bis(β-carbamoylethyl)ethylenediamine, N,N′-bis(β-carbamoylethyl)trimethylenediamine, N,N′-bis(β-carbamoylethyl)-1,2-propylenediamine, and N,N′-bis-(β-carbamoylethyl)-2-hydroxyltrimethylenediamine were determined potentiometrically in 0.10 mol dm^?3 NaNO₃ at 25.0°C. The formation of Cu(II) complexes of these ligands and the CuO to CuN bond rearrangements at the two amide sites of these complexes were investigated quantitatively by potentiometric and spectrophotometric techniques under the same conditions. Electronic spectra of the Cu(II) complexes of these ligands and their deprotonated species formed in aqueous solution were measured and discussed.     

Excess enthalpies of binary and ternary mixtures of acetonitrile with methanol,ethanol and benzene

Excess molar enthalpies are measured for the binary mixtures methanol—acetonitrile and ethanol—acetonitrile at 25 and 35°C and for the ternary mixtures methanol—acetonitrile—benzene and ethanol—acetonitrile—benzene at 25°C using an isothermal dilution calorimeter. The binary results are well reproduced with an association model which contains four equilibrium constants for the association of alcohol, two equilibrium constants for that of acetonitrile, and two solvation equilibrium constants between alcohol and acetonitrile molecules. The ternary results are compared with those calculated from the model with binary parameters.     

Spectroscopic and scattering investigation of isopoly-molybdate and tungstate solutions

Detailed spectroscopic and scattering investigations of isopoly-molybdate and -tungstate solutions as a function of concentration and pH were made. From scattering results the apparent molecular weights were determined as a function of time and concentration. We find that the result agree with the aggregation scheme of simple → hepta → octa → [Mo₃₆O₁₁₂]^?8 → protonated polymeric species, for molybdate solutions. Tungstate solutions aggregate according to simple → Y-polytungstate → paratungstate-A → paratungstate-B → Ψ-metatungstate. The molybdate solutions exhibited very rapid equilibration, but the tungstate solutions required several days to reach equilibrium. From the discrete changes in the Raman spectra of both systems we find that the formation of isopoly anions is not a continuous process and that only certain species are present in solution. Our results do not rule out the formation of significant quantities of the octamolybdate anion as suggested by previous investigators.     

Hydrates of sodium thiosulphate

Dehydration of sodium thiosulphate pentahydrate with organic solvents produces mixtures of the anhydrous salt and dihydrate for compositions up to 2H₂O and of di- and pentahydrates above this composition, with occasional traces of monohydrate present. This confirms the stable compounds in the Na₂S₂ O-H₂O system. The constituents in mixtures were identified qualitatively and semi-quantitatively by Raman spectroscopy. X-ray powder diffractometry is much inferior for identification purposes. Correlations between vibrational frequencies and structure are suggested.     

Ionic equilibria in ferric sulfate-sulfuric acid solutions

The ionic equilibria of ferric sulfate-sulfuric acid aqueous solution are modeled mathematically, taking into account the effect of ionic strength. Results of this analysis indicate that ion interactions can significantly change the ionic concentration of the solutions which could lead to errors in the evaluation of data on iron(III) extraction kinetics or equilibrium.     

Studies on yellow and colourless molybdophosphate complexes in the aqueous solution by laser raman spectroscopy

Yellow and colourless complexes of molybdophosphate were investigated by the use of laser Raman spectroscopy. Two kinds of yellow molybdophosphates were identified in the weakly acidic solutions: 12-molybdophosphoric and 11-molybdophosphoric acid which are in equilibrium in solution at pH 1-2. When excess phosphate is present, the colourless molybdophosphate is formed. This complex exists in the solutions of pH 4-1 under the condition of excess phosphate ([P]/[Mo] > 2). This complex was confirmed to be P₂Mo₅O^6?₂₃ and is so stable that the yellow molybdophosphate is converted into the colourless by excess phosphate.     

Methyl group exchange in methyllithiumlithium bromide solutions in diethyl ether

The 220 MHz ¹H NMR spectrum of an ether solution of CH₃Li and LiBr in 10–1 ratio has been examined as a function of temperature. At low temperature distinct resonances, assignable to Li₄(CH₃)₄ and Li₄(CH₃)₃Br, are seen. Methyl group exchange between the two tetramers is observed in the NMR spectra in the temperature interval ?32 to 0°. The exchange is shown to be much slower than the dissociation of Li₄(CH₃)₄ tetramer, measured in other work. It is proposed that the rate-determining step is dissociation of Li₄(CH₃)₃Br to form Li₂(CH₃)₂ and Li₂(CH₃)Br. The rate constant for dissociation, k₂, obeys the equation ln k₂ = 36.0?83303/T.     

Spectrophotometric and potentiometric study of the cobalt(II)-thiocyanate system in aqueous medium

The cobalt(II)—thiocyanate system was spectrophotometrically studied at 2.0 M ionic strength (NaClO₄) and 25°C. The following formation constants were obtained: β₁ = 6.9 M^?, β₂ = 28.9 M^?2, β₃ = 12.1 M^?3 and β₄ = 1.30 M^?4. Three wavelengths were considered, 515, 590 and 615 nm, and the molar absorptivities of each species were calculated. Linear relationships were obtained for $\text{ε}$ vs $\text{n}$ and α_i. There is strong evidence that the tetrahedral [Co(SCN)₄]^2? is virtually the only species absorbing at 590 and 615 nm. An indirect potentiometric method led to comparable equilibrium constants. The cadmium(II)—thiocyanate formation constants used in the indirect method, under the same conditions, were found to be β₁ = 21.51 ± 0.09 M^?1, β₂ = 123 ± 1 M^?2, β₃ = 130 ± 3 M^?3 and β₄ = 173 ± 1.2 M^?4, in good agreement with earlier literature data.     

On the tri-n-octylammonium chloro complexes of Cu(II), Zn(II) and Co(II) in benzene solution

Extracts with tri-n-octylammonium chloro complexes of Cu(II), Zn(II) and Co(II) of various compositions, including the N-deuterated compounds, were prepared and investigated by IR spectroscopy and conductivity measurements. Besides the well-known 2:1-complexes (TOAH⁺)₂MCl₄^2?, for which new assignments of νNH frequencies are given, complexes with a stoichiometric ratio TOA:M > 2 were found. Their cations contain the groups (TOAH …Cl…HTOA)⁺ and TOAH⁺ and they are supposed to be 3:1-complexes (TOAH…Cl…HTOA)⁺TOAH⁺MCl₄^2?. The IR spectrum of the 1:1-complex TOAH⁺CuCl_3? is given. The occurrence of the analogous 1:1-complex TOAH⁺ZnCl_3? could not be detected under the preparative conditions used.     

ESR studies on the reactions of sulphite radical anion,SO3.̄−, with nitroalkane compounds in aqueous solutions

The reactions of the sulphite radical anion, SO₃^{$\text{.}\text{?}$?} (generated from the Ti³⁺-H₂O₂-Na₂SO₃ system at pH 9), in aqueous solutions with some nitroalkane compounds were investigated by using a rapid-mixing flow technique coupled with electron spin resonance (ESR) which can detect the radicals having a lifetime of 5–100 ms. The SO₃^{$\text{.}\text{?}$?} radical added to the double bond of CN in the nitroalkane aci-anions which are the main form of nitroalkanes in aqueous alkaline solutions. From the observed hyperfine splitting constants of the SO₃^{$\text{.}\text{?}$?} adducts of nitroalkane aci-anions, the preferred conformation of the adducts was deduced.     

Studies on the intermolecular interactions of metal chelate complexesVIII: On the interactions of dithiocarbamato-copper(II) and -copper(I) complexes with haloalkanes

The interaction of Cu(II)(dtc)₂ and Cu(I)(dtc) complexes with haloalkanes were studied by the EPR method. It was found that the Cu(II)(dtc)₂ complex reacted with haloalkanes only in the presence of weak Lewis bases which formed adducts with it. The intermediate reaction product is the mixed-ligand complex Cu(II)(dtc)X_n (X = Cl, Br, n = 1 or 2); the final products being CuX₂B_n (B = Lewis bases, n = 1 or 2) and unstable resin-like residue. Cu(I)(dtc) reacted with haloalkanes without any promoters giving the mixed-ligand complex Cu(II)(dtc)X_n as product. Free radicals were detected in the reaction of Cu(I)(dtc) using the method of “radical scavenger” and were not found in the reaction of Cu(II)(dtc)₂. The reported results confirmed one of the two reaction mechanisms proposed in the previous studies. The role of the solvent on the EPR parameters of the mixed-ligand Cu(II)(dtc)X complex is also discussed.