Electrical conductance,density and viscosity of the system lead(II) dodecanoate/dodecanoic acid

Data are presented for the densities, electrical conductances and viscosities of the molten system lead(II) dodecanoate/dodecanoic acid. Over the concentration range studied, molar volumes are linear functions of concentration at any selected temperature, although there are indications of deviations from ideal behaviour over the complete composition range from pure soap to pure acid. The molar volumes of the system lead(II) carboxylate/carboxylic acid for the even chain acids C₁₀ to C₁₈ are linear functions of chain length. As with other lead(II) dodecanoate systems, the Arrhenius plots for the conductance of the mixtures show curvature.Activation energies for conductance in the low temperature region show a steady decrease with increasing mole fraction of the acid. It is suggested that this arises largely from the increased mobility of the Pb²⁺ ion. The activation energies for viscous flow in the mixtures are similar to that of pure lead dodecanoate. Studies of the viscosities of the system lead(II) carboxylate/carboxylic acid as a function of the temperature for the even chain length acids C₁₀ to C₁₈ suggest a slight decrease in size of the unit of viscous flow when acid is present.     

The densities and molar volumes of molten lead(II) dodecanoate/dodecanoic acid mixtures over their complete composition range: Evidence for non-ideal behaviour

Data are presented for the densities and molar volumes of the molten system lead(II) dodecanoate/dodecanoic acid over its complete composition range. For equimolar mixtures, plots of molar volume against temperature show curvature at high temperatures, suggesting deviations from ideal behaviour. Support for this comes from a plot of molar volume at constant temperature against acid mole fraction. Densities and molar volumes are reported for lead (II) carboxylate/carboxylic acid (0.5 mole fraction) and for pure carboxylic acid for the even chain acids C₁₀ to C₁₈. The molar volumes at constant temperature in these cases are linear functions of chain length, although the volume occupied per methylene group in equimolar mixtures is suggested to be slightly smaller than with pure soap or pure acid. An explanation for non-ideal behaviour becoming more marked at higher temperature is given in terms of acid monomer-dimer equilibria.     

207Pb N.M.R. of lead(II) soaps in solid,liquid-crystalline and liquid phases

Abstract

²⁰⁷Pb N.M.R. data are reported for a number of even chain length lead(II) carboxylates (soaps) at various temperatures. At room temperature, the solid lead(II) decanoate and tetradecanoate show similar spectra, with a single metal ion site, and modest shielding anisotropy. As the temperature is increased, the soaps (hexanoate to octadecanoate) all form a highly ordered smectic phase, which gives a very broad ²⁰⁷Pb signal of linewidth comparable to that of the solid phase. At higher temperatures, the hexanoate to dodecanoate soaps form a lamellar L _α (smectic A) phase, whilst the longer chain length carboxylates melt directly to the liquid phase. Both the lamellar L _α and liquid phase give fairly sharp, isotropic signals, whose chemical shifts and linewidths are strongly temperature dependent. Possible explanations for this effect include paramagnetic contributions to the shielding tensor from low-lying electronic states of Pb(II), and contributions to the observed signal from different coordination species produced in the lead(II) carboxylate system. Although there are discrete changes in chemical shift at the phase transition, the magnitudes observed in all the phases are similar, suggesting that there are no dramatic changes in the metal coordination environment.     

Properties of molten carboxylates part 5. A quantitative differential thermal analysis study of mesophase formation in the sytems lead(II)dodecanoate/lead(II) oxide and lead(II)dodecanoate/hendecane

Measurements have been made of the temperatures and enthalpy changes of phase transitions in the systems lead dodecanoate/lead oxide and lead dodecanoate/hendecane. The data have been discussed in terms of the R theory of amphiphylic mesophases. The concepts of the R theory are shown to be useful in the interpretation of phase transitions in molten carboxylate systems.     

Thermal behaviour of the system lead(II) dodecanoate/lead acetate

Data are presented for the heats and entropies of phase changes for the system lead(II) dodecanoate/lead acetate. A phase diagram has also been constructed for the system.Optical observation under a polarising microscope suggests that the phase sequence in this system is the same as in pure lead dodecanoate i.e. crystal → G (smectic) → V₂ (cubic isomorphous) → liquid.The entropy of the V₂ → liquid transition in the mixtures is the same as for pure lead dodecanoate which suggests that addition of lead acetate to lead dodecanoate does not affect the state of aggregation of the soap in the liquid phase.     

Effects of Samarium on the Properties of the Anodic Pb（Ⅱ） Oxides Film Formed on Pb in Sulfuric Acid Solution

The effects of samarium on the properties of the anodic Pb(II) oxides films formed on lead at 0.9 V (vs. Hg/Hg₂SO₄) in 4.5 mol/L H₂SO₄ solution were studied using linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and scanning electron micrographs (SEM). The experimental results show that adding Sm to lead metal can inhibit the growth of the Pb(II) oxides film effectively, and reduce the resistance of the PbO oxides film obviously. The addition of Sm increases the porosity of the anodic film, which may cause the increase of the ionic conductance produced by the interstitial liquid among the PbO particles in the film and lead to the decrease of the resistance of the anodic film.     

Kinetics and reaction mechanism for the thermal decomposition of some even chain lead(II) carboxylates

The kinetics of the thermal decomposition of lead(II) dodecanoate, tetradecanoate and octadecanoate have been studied thermogravimetrically in the temperature range 298–1073 K by the modified method of Freeman and Carroll. The thermogravimetric curves show that while the octadecanoate decomposes in one single step to lead oxide, the dodecanoate and tetradecanoate decompose in two stages to lead oxide. The kinetic results show all the reactions, except the second step breakdown of dodecanoate (which is nearly unity), to be of zero order. Activation energy values are presented for the desorption of carbon dioxide and the diffusion controlled rate of formation of a degradative intermediate identified as a ketone. Tentative mechanisms are advanced to explain the degradative route of these compounds.     

Zinc(II) and lead(II) coordination polymers built by 3-(4-carboxyphenylhydrazono)pentane-2,4-dione

Two coordination polymers [Zn(L)₂(4,4′-bipy)₂] _n (4,4′-bipy = 4,4′-bipyridine) (1) and [Pb(η ²-L)(µ₃-η ²-CH₃COO)(H₂O)] _n (2) have been prepared by the reaction of 3-(4-carboxyphenylhydrazono)pentane-2,4-diketone (HL) with zinc(II) or lead(II) in solution. Polymer 1 shows an infinite zigzag chain, in which Zn(II) are linked by 4,4′-bipy bridges with carboxylate of L^? monodentate to Zn(II). In 2, Pb(II) are bridged by tetradentate µ₃-η ²-CH₃COO^? to form a linear 1-D chain, and each Pb(II) is chelated by carboxylate of L^?. Their molecular structures have been characterized by elemental analysis, infrared, and single-crystal X-ray diffraction. Thermal and fluorescent properties of the two complexes have been investigated.     

Novel lead(II) carboxylate-arsonate hybrids

Hydrothermal reactions of lead(II) acetate with phenylarsonic acid (H₂L¹) (or 4-hydroxy-3-nitrophenylarsonic acid, H₃L²) and 5-sulfoisophthalic acid monosodium salt (NaH₂SIP) (or 1,3,5-benzenetricarboxylic acid (H₃BTC)) as the second metal linkers afforded three novel mixed-ligand lead(II) carboxylate-arsonates, namely, Pb₅(SIP)₂(L¹)₂(H₂O) 1, Pb₃(SIP)(L²)(H₂O) 2 and Pb(H₂L²)(H₂BTC) 3. The structure of 1 features a complicated 3D network composed of 2D double layers of lead(II) sulfoisophthalate bridged by 1D chains of lead(II) arsonates along b-axis, forming large tunnels along b-axis which are occupied by phenyl rings of the arsonate ligands. In 2, the Pb(II) ions are bridged by {L²}³⁻ anions into a 2D double layer whereas the interconnection of the Pb(II) ions via bridging and chelating SIP anions gave a 2D double layer. The cross-linkage of the above two building units leads to a complicated 3D network. In 3, the interconnection of the Pb(II) ions via bridging {H₂L²}⁻ and {H₂BTC}⁻ anions leads to a 1D double chain down a-axis. These 1D chains are further interconnected via hydrogen bonds among non-coordination carboxylate groups and arsonate oxygens into a 3D supramolecular architecture.     

Solution behaviour of lead(II) carboxylates in organic solvents

The solution behaviour has been studied of a series of even chain length lead(II) carboxylates (octanoate to octadecanoate) and the odd chain length lead(II) heptadecanoate in a variety of non-complexing organic solvents and in alcohols. In agreement with previous studies, solubility increases dramatically above a certain temperature, which depends on solute concentration, chain length and solvent. This solution temperature is also affected by traces of water. These results are complemented by studies using vapour pressure osmometry, dynamic light scattering, ¹H and ¹³NMR spectroscopy. The results in water-free systems are consistent with the formation of rather ill-defined, polydisperse aggregates, which increase in size with concentration and decrease with temperature. These show similar local structure to lamellar mesophases in the pure lead(II) carboxylates, and are suggested to be formed by solvent induced swelling and break-up of these mesophases. In the presence of water, a more ordered structure is formed, in which a few water molecules are suggested to be bound to the lead(II) carboxylate headgroup.     

Mesophase formation in lead(II) decanoate

Abstract

Structures of the thermotropic mesophases of lead(II) decanoate are reassigned following optical and X-ray diffraction studies. These results, and those of D.S.C., Raman and ²⁰⁷Pb N.M.R. spectroscopy, indicate formation of a lower temperature mesophase involving mainly increased lateral disorder, and a higher temperature L_α (smectic A) phase resulting from chain disordering and decreased lead-carboxylate interaction. Comparison of experimental thermodynamic data for the phase transitions with theoretical data in the literature indicates that the entropy change for the lower to higher mesophase transition is dominated by the increase in chain disorder.     

Reactions of nanoparticles inside a polyethylene matrix: Reduction of lead(II) and mercury(II) oxides by supercritical isopropanol

Methods were developed for manufacturing of isolated nanoparticles of lead(II) and mercury(II) oxides produced by the thermal decomposition of metal compounds in a solution-melt of low-density polyethylene (LDPE) in mineral oil. The PbO and HgO nanoparticles stabilized in the LDPE matrix were characterized using X-ray powder diffraction and transmission electron microscopy (TEM). The metal oxides in the polyethylene matrix were reacted with a supercritical fluid of isopropanol (SCF i-PrOH). The PbO in the nanoparticles was reduced to the metal as a result of the reaction with SCF i-PrOH. When SCF i-PrOH was reacted with the HgO nanoparticles stabilized in the LDPE matrix, the oxide was also reduced to the metal. TEM showed that the nanoparticles were conserved after their reaction with SCF i-PrOH.     

Complexes of dicamba with cadmium(II), copper(II), mercury(II), lead(II) and zinc(II)

New solid complexes of a herbicide known as dicamba (3,6-dichloro-2-methoxybenzoic acid) with Pb(II), Cd(II), Cu(II) and Hg(II) of the general formula M(dicamba)₂·xH₂O (M=metal, x=0-2) and Zn₂(OH)(dicamba)₃·2H₂O have been prepared and studied. The complexes have different crystal structures. The carboxylate groups in the lead, cadmium and copper complexes are bidentate, chelating, symmetrical, in Hg(dicamba)₂·2H₂O - unidentate, and in the zinc salt - bidentate, bridging, symmetrical. The anhydrous compounds decompose in three stages, except for the lead salt whose decomposition proceeds in four stages. The main gaseous decomposition products are CO₂, CH₃OH, HCl and H₂O. Trace amounts of compounds containing an aromatic ring were also detected. The final solid decomposition products are oxychlorides of metals and CuO. This revised version was published online in July 2006 with corrections to the Cover Date.     

New lead(II) catecholate and o-semiquinone complexes

Lead(II) catecholate complexes were prepared by reduction of 3,6-di-tert-butyl-o-benzoquinone and its derivatives with lead metal in THF. The molecular structure of the (CatPb)₄·(PbO)₂·6C₃H₆O complex (Cat is the dianion of 3,6-di-tert-butylcatechol), which was synthesized by hydrolysis of lead 3,6-di-tert-butylcatecholate in acetone, was established by X-ray diffraction. A series of lead(II) o-semiquinone complexes, which were prepared by the addition of the phenoxyl radical to lead catecholates or by oxidation of the latter with mercury(II), copper(II), or silver(I) halides, were studied by the ESR method. Lead(II) mono-o-semiquinolate complexes undergo symmetrization to form stable bis-o-semiquinolates, which were isolated and characterized in individual state. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1103–1111, July, 2006.     

Syntheses, characterizations and crystal structures of two new lead(II) amino and carboxylate-sulfonates with a layered and a pillared layered structure

Reactions of lead(II) acetate with m-aminobenzenesulfonic acid (HL¹) and 5-sulfoisophthalic acid (H₃L²) afforded two new lead(II) sulfonates, Pb(L¹)₂1 and Pb₂(L²)(μ₃-OH)(H₂O) 2. In compound 1, the lead(II) ion is eight-coordinated by two sulfonate groups bidentately, two sulfonate groups unidentately and two amino groups from six ligands. Each L¹ ligand is tetradentate and bridges with three Pb(II) ions. The interconnection of the Pb(II) ions via bridging sulfonate ligands resulted in 〈100〉 and 〈200〉 layers. In compound 2, one Pb(II) ion is six-coordinated by a carboxylate group bidentately, by two carboxylate groups unidentately, by a sulfonate oxygen atom and by an OH anion, whereas the other one is six-coordinated by a bidentate chelating carboxylate group, two μ₃-OH anions, a sulfonate oxygen atom and an aqua ligand. The interconnection of irregular PbO₆ polyhedra via carboxylate-sulfonate ligands resulted in the formation of a pillared layered structure with the 2D layer being formed; the lead(II) ions, hydroxyl groups, carboxylate and sulfonate groups and the benzene ring as the pillar agent.     

Two isomeric lead(II) carboxylate-phosphonates: syntheses, crystal structures and characterizations

Two isomeric layered lead(II) carboxylate-phosphonates of N-(phosphonomethyl)-N-methyl glycine ([MeN(CH₂CO₂H)(CH₂PO₃H₂)]=H₃L), namely, monoclinic Pb₃L₂·H₂O 1 and triclinic Pb₃L₂·H₂O 2, have been synthesized and structurally determined. Compound 1 synthesized by hydrothermal reaction at 150°C is monoclinic, space group C2/c with a=19.9872(6), b=11.9333(1) and c=15.8399(4) Å, β=110.432(3)°, V=3540.3(1) Å³, and Z=8. The structure of compound 1 features a 〈400〉 layer in which the lead(II) ions are bridged by both phosphonate and carboxylate groups. The lattice water molecules are located between the layers, forming hydrogen bonds with the non-coordinated carboxylate oxygen atoms. Compound 2 with a same empirical formula as compound 1 was synthesized by hydrothermal reaction at 170°C. It has a different layer structure from that of compound 1 due to the adoption of a different coordination mode for the ligand. It crystallizes in the triclinic system, space group with cell parameters of a=7.1370(6), b=11.522(1), c=11.950(1) Å, α=110.280(2), β=91.625(2), γ=95.614(2)°, V=915.3(1) Å³ and Z=2. The structure of compound 2 features a 〈020〉 metal carboxylate-phosphonate double layer built from 1D lead(II) carboxylate chains interconnected with 1D lead(II) phosphonate double chains. XRD powder patterns of compounds 1 and 2 indicate that each compound exists as a single phase.     

Cymantrenecarboxylate complexes of nickel(II) and cobalt(II)

Reactions of cymantrenecarboxylic acid (CO)₃MnC₅H₄COOH (CymCOOH) with Ni(II) and Co(II) pivalates in boiling THF followed by extraction of the products with diethyl ether or benzene and treatment with triphenylphosphine gave the binuclear complexes LM(CymCOO)₄ML (M = Ni (I) and Co (II); L = PPh₃). Treatment of the benzene extract of the intermediate cobalt cymantrenecarboxylate with 2,6-lutidine (L’) yielded the trinuclear complex L’Co(CymCOO)₃Co(CymCOO)₃CoL’ (III). Complex I is antiferromagnetic; μ_eff decreases from 3.7 to 0.9 μ_B in a temperature range from 300 to 2 K. Structures I-III were identified using X-ray diffraction. The frameworks of complexes I and II are like Chinese lanterns, having four carboxylate bridges and axial ligands L (Ni-P, 2.358(1) Å; Co-P, 2.412(2) Å). The metal atoms are not bonded to each other (Ni…Ni, 2.7583(9) Å; Co…Co, 2808 (2) Å). In complex III, either terminal Co atom is coordinated to one ligand L’ (Co-N, 2.059(2) Å). The Co atoms form a linear chain showing no M-M bonds (Co…Co, 3.346(1) Å), in which either terminal Co atom is linked with the central Co atom by three carboxylate bridges (on average, Co_centr-O, 2.164 Å; CO_term-O, 2.094 Å). In one of three carboxylate groups, only one carboxylate O atom serves as a bridge, while the other is bonded to the terminal Co atom only (Co_term-O, 2.094 and 2.389 Å); so this carboxylate group is a bridging and chelating ligand.     

Studies on complexes of metal(II) carboxylates with donor molecules,part III. Complexes of cobalt(II) alkanoates with aromatic amineN-oxides

Summary Cobalt(II) propionate and n-butyrate react with pyridineN-oxide, 3-methylpyridineN-oxide and quinolineN-oxide in methanol to give solid [Co(O₂CR)₂ · L]₂ complexes which have been shown by elemental analysis, conductance, molecular weight, magnetic and spectral studies to be octahedral, binuclear, carboxylate bridged species. The complexes exhibit low magnetic moments at room temperature.     

Effects of Samarium on the Properties of the Anodic Pb(II) Oxides Film Formed on Pb in Sulfuric Acid Solution

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X-ray irradiation-assisted low-temperature synthesis of yellow lead(II) oxide (massicot) in aqueous solution

Processes occurring in the lead(II)-hydroxide anion system in aqueous solutions at pH > 12 and an ambient temperature (20–25°C) irradiated simultaneously with X-rays at a wavelength of 0.01–1.0 nm were considered. It was shown that the yellow polymorph of the oxide PbO (massicot) precipitated from the solution after a relatively short period of time under the given specific conditions, a development that can be of use for the manufacture of this compound.