A new family of the 3D heterometallic coordination polymers [{Ln2(SO4)2(H2O)2(pydc)2Cu2 (bpy)2·2(H2O)}]n (Ln = Sm ( 1), Eu ( 2), Gd ( 3), Tb ( 4) and Dy ( 5); pydc = 2,6-pyridine-dicarboxylate anion; bpy= 4,4-bipyridine) have successfully been synthesized under solvothermal conditions (H2O/ethanol). All the coordination polymers obtained were characterized by elemental analysis, FT-IR analysis, differential thermal analysis/thermogravimetry (DTA/TG), fluorescent spectra and single crystal X-ray diffraction analysis. The most intriguing structural feature is that all the compounds exhibit 3D frameworks with 1D inorganic lanthanide ladders and organic CuI-bipyridine chains, which represent two types of 3d/4f coordination polymers (form I: Ln = Sm and Eu; form II: Ln = Gd, Tb and Dy) as the result of a so-called gadolinium break effect. Additionally, compounds 2 and 4 showed the characteristic emission spectra of the EuIII and TbIII ions, respectively, and appeared to have good fluorescence properties, while 1, 3 and 5 emitted fluorescence resembling CuI complexes. To our knowledge, the investigation of the
A comparative study of polynuclear thallium complexes with dialkyldithiocarbamates [Tl2{S2CNR2} 2]n (R = CH3, i-C3H7, C4H9, and i-C4H9; R2 = (CH2)6) was performed by solid-state 13C and 15N CP/MAS NMR spectroscopy. The dithiocarbamate groups were found to be structurally equivalent in the complexes studied. An increase in the positive inductive effect of alkyl substituents at the N atom increased 15N chemical shifts as a result of a combination of positive inductive effect of the alkyl substituents and the mesomeric effect of =NC(S)S-groups. The first representative of thallium(I) complexes with a cyclic dithiocarbamate ligand [Tl2{S2CN(CH2) 6}2]n was obtained. Its molecular structure was determined from X-ray diffraction data. The β-form of the isotope-substituted complex [63/65CuTl2{S 2CN(CH2)6}4] was obtained and examined by EPR spectroscopy. The EPR spectra were modeled at the second order of the perturbation theory. The spin density at the thallium atoms was calculated and its distribution over the AOs of thallium was determined.
Heat treatment of Y-TZP at high temperatures produces materials with a mixed Y-TZP/PSZ phase assemblage, which exhibit a unique combination of high mechanical strength and fracture toughness, uncommon in zirconia ceramics. The microstructure and crack growth resistance of the Y-TZP/PSZ materials developed by treating at 1650°C in air a fine-grained Y-TZP was studied. XRD as well as Raman spectroscopy results indicate that the obtained microstructure allow the retention of large tetragonal grains (up to ˜4 μm), resulting in both phase transformability enhancement and pronounced R-curve behavior. The large transformation zone, discerned from accurate measurements with Raman microprobe spectroscopy, sustains the above assessment and points out tetragonal to monoclinic phase transformation as the main toughening mechanism in the investigated Y-TZP/PSZ microstructures. This was confirmed by satisfactory agreement between the transformation toughening estimated from numerical analysis and the crack shielding experimentally determined from the R-curve measurements.
Flotation kinetics of pentlandite and violarite contained in copper-nickel ores and the effect of crystallochemical peculiarities of the minerals on their flotation features are studied. Studies of the effect of pentlandite crystallochemical features on its flotation properties have shown that the easiest to float is nickel-enriched pentladite, cobalt-enriched one being somewhat worse the worst being iron-enriched one. Pentlandite was found to be much better recovery to flotation concentrates than violarite. So, the process of violaritization of the surface of pentlandite grains, which may occur during the flotation, will negatively affect its characteristics.
In this paper, the acid-base properties of illite/water suspensions are examined using the constant capacitance surface complexation model. On the basis of results of potentiometric titrations and solubility experiments, we conclude that the proton reactions in the supernatants of illite suspensions can be successfully represented by proton reactions of Al(H2O)63+and Si(OH)4in water solutions. For illustrating the acidic characteristics of aqueous illite surfaces, two surface protonation models are proposed: (1) one site-one pKamodel, ≡SOH ≡SO-+ H+, pKaint= 4.12-4.23; (2) two sites-two pKas model, ≡SIOH ≡SIO-+ H+, pKintaI= 4.17-4.44, and ≡SIIOH ≡SIIO-+ H+, [dipKintaII= 6.35-7.74. Evaluation of these two models indicates that both of them can give good descriptions of the experimental data of systems with different illite concentrations and ionic strengths and that the one site-one pKa model can be considered as a simplification of the two sites-two pKas model. Since both models assume only deprotonation reactions at the illite surfaces, they suggest that the surface behavior of the illite is similar to that of amorphous SiO2. Model assumptions, experimental procedures, and evaluative criteria are detailed in the paper.
In this paper, we conducted potentiometric titrations, batch adsorption experiments and FT-IR analysis to study the uptake of copper in illite/water suspensions and then applied the constant capacitance surface complexation model to interpret the reaction mechanism at the aqueous illite surfaces. Our research shows that the copper adsorption at these surfaces is strongly dependent on pH and that the adsorption causes a deprotonation of surface groups. We propose that the uptake of copper in the carbonate-free illite suspensions can be explained by the formation of mononuclear surface complexes, ≡SOCu+ and ≡SOCuOH, and a multinuclear surface complex, ≡SOCu2(OH)2+, followed by the formation of a bulk precipitate, Cu(OH)2(s), or a surface precipitate, ≡SOCu2(OH)3(sp). For the illite suspensions containing carbonates, we propose that the copper-illite interaction can be depicted by the formation of mononuclear surface complexes, ≡SOCu+and ≡SOCuOH, followed by the formation of a copper hydroxylcarbonate precipitate, Cu2(OH)2CO3(s), rather than a copper hydroxide precipitate. The existence of Cu2(OH)2CO3(s) in the carbonate-containing illite suspensions was identified by FT-IR analysis.
As part of an extended project to illustrate how heavy metals are complexed by natural aquatic particles, we conducted various experiments to study the adsorption of fulvic acid (FA) at aqueous illite surfaces and the complexation of heavy metal copper(II) in illite-FA bi-complexant systems. By analyzing batch adsorption and potentiometric titration data, we found that (i) the adsorption of FA by illite decreases with increases in pH values and its pH adsorption edge resembles those of SiO2-FA and montmorillonite-FA systems described by other researchers, (ii) it is possible to effectively simulate the complexation of Cu2+ ions in illite-FA bi-complexant systems by taking it to be an additive complexation of two mono-complexant systems (FA-Cu2+ and illite-Cu2+) and (iii) FA can inhibit the retention of heavy metals at solid surfaces by forming soluble complexes with metal ions. The above results and conclusions are supported by FT-IR analysis of various illite-FA-Cu2+ systems.
The prospects for near-IR-excited Raman scattering from cement minerals are discussed, and a very unusual result concerning the intensity of the spectra is presented.
The hydration of γ-Al2O3 has been studied by Fourier transform (FT) Raman and infrared (IR) spectroscopy, and by X-ray diffraction (XRD). The initial findings are presented, along with a discussion of the possible causes for the major spectral changes that occur after hydration. The aims of the study and ongoing research are described.
Surface complexation modelling is introduced to investigate the surface reactions in a mixed galena and sphalerite flotation system. Computer-assisted calculations based on surface complexation modelling (SCM) are performed to obtain the mineral surface distribution of ethyl xanthate as well as carbonate and excess sulphide ions as a function of pH. The significance of pe is demonstrated by computing the mineral surface speciation in a flotation system with xanthate and excess of sulphide ions. The results are used to evaluate the influences of pH, pe, the concentration of xanthate, sulphide or carbonate ions to the mineral flotability. The flotation mechanisms in galena-sphalerite system are discussed based on SCM.
The adsorption of H+, OH- and ARS (Alizarin Red S) onto hydrous fluorapatite surfaces and Ca2+-ARS complexation in solution were studied by means of combined potentiometric and spectrophotometric titrations, as well as zeta potential and FT-IR measurements. Corresponding equilibrium constants of surface and solution reactions are determined. The application in flotation processes is discussed.
In the present study infrared attenuated total reflection (IR-ATR) was used to monitor the rate of in situ adsorption of heptyl xanthate on a layer of zinc sulfide synthesised on a germanium ATR crystal. The zinc sulfide surface was characterised using x-ray photoelectron spectroscopy (XPS). The absorbance of heptyl xanthate measured increased with increasing bulk concentration of the adsorbate up to an equilibrium plateau value corresponding to a fractional coverage of the surface sites of the substrate. For the adsorption from solutions of concentrations between 10-3 and 10-5 M, the rate of adsorption increased with increasing bulk concentration. At higher concentrations the measured absorbance should be corrected for the absorbance due to the concentration of xanthate in bulk solution. The present work provides a discussion of this correction. Assuming the adsorption stage to be rate-controlling and proportional both to the concentration of the adsorbing species in solution and unreacted surface area, a rate law governing this type of transient adsorption kinetics was derived. By means of absorbance data for the concentrations 0.1 and 0.01 mM, die rate constant of adsorption was calculated. From the initial part of a Langmuir adsorption isotherm, the absorbance at monolayer coverage and the equilibrium constant of adsorption could be estimated.
In the present study infrared attenuated total reflection (IR-ATR) was used to monitor the rate of in situ adsorption of heptyl xanthate on a layer of zinc sulphide synthesized on a germanium ATR crystal. The zinc sulphide surface was characterized using X-ray photoelectron spectroscopy (XPS). The absorbance of heptyl xanthate measured increased with increasing bulk concentration of the adsorbate up to an equilibrium plateau value corresponding to a fractional coverage of the surface sites of the substrate. For the adsorption from solutions of concentrations between 10−3 and 10−5 M, the rate of adsorption increased with increasing bulk concentration. At higher concentrations the measured absorbance should be corrected for the absorbance due to the concentration of xanthate in bulk solution. The present work provides a discussion of this correction. Assuming the adsorption stage to be rate-controlling and proportional both to the concentration of the adsorbing species in solution and unreacted surface area, a rate law governing this type of transient adsorption kinetics was derived. By means of absorbance data for the concentrations 0.1 and 0.01 mM, the rate constant of adsorption was calculated. From the initial part of a Langmuir adsorption isotherm, the absorbance at monolayer coverage and the equilibrium constant of adsorption could be estimated.
Raman spectra of kaolinite and of the formamide-intercalated kaolinite were obtained at both 298 and 77 K using a Raman microprobe equipped with a thermal stage. Upon cooling to 77 K, the band attributed to the inner hydroxyl shifts by 5 cm-1 to lower wavenumbers and the bands assigned to the inner surface hydroxyls move to higher wavenumbers. Upon intercalation of the kaolinite with formamide, an additional Raman band attributed to the formation of a hydrogen-bonded complex between the inner surface hydroxyls and the carbonyl group of the formamide is observed at 3627 cm-1 at 298 K and at 3631 cm-1 at 77 K. Raman spectra of the deintercalation of the formamide-intercalated kaolinite are obtained by using the thermal stage to heat the intercalated kaolinite in situ. A decrease in intensity of the bands formed through intercalation and at the same time an increase in intensity of the inner surface hydroxyl bands are observed. A loss of intensity of the low-wavenumber region of the formamide-intercalated kaolinite is also observed.
The interaction of dextrin with colloidal ZnS has been investigated through adsorption studies and FT-IR spectroscopy in the 4000-400 cm-1range. The adsorption capacity is estimated to be around 1 mg/m2. Maximum adsorption is found to be constant below pH ≈7 and to increase with pH at least up to pH 11. Eighty percent of maximum adsorption is achieved within 3 min after addition of the dextrin. Based upon FT-IR studies and titration data, an adsorption mechanism is proposed.
The surface complexes of colloidal ZnS have been studied using FT-IR and FT-Raman techniques. The absorption bands at 2500 and 1475-1375 cm-1, which are identified as the S-H bond and the Zn-OHCO2 entity, respectively, can be observed under varied conditions of sample stoichiometry and pH. The correlation between surface spectra and the complexation model is evaluated. The relation between the intensities of FT-IR and FT-Raman spectra and particle size is discussed.
A SERS active substrate is created on a non-SERS active oxidized aluminium foil. Identification of phthalic acid and phenylphosphate using near infrared FT-SERS is made and possible orientations are proposed.
On the basis of the theory of SER spectra, proposed in a previous paper, the SER spectra of 1,3,5-trifluorobenzene, 1,3,5-trideuteriobenzene, benzene and hexafluorobenzene are analysed. It is demonstrated that the bands, caused by the totally symmetric modes and by the mode transforming as the d(z) moment experience large enhancement. The existence of a large number of forbidden bands in the SER spectra is pointed out. Some anomalies in the enhanced spectra are explained by qualitative ideas and by the 'interference phenomenon' of various contributions. It is pointed out that all the observed lines and regularities of the SER spectra can be explained within the framework of the quadrupole and dipole electrodynamical mechanism of the enhancement.
The diffuse reflectance infrared Fourier transform (DRIFT) technique was used to study sodium 1,2-dihydroxyanthraquinone-3-sulphonate (ARS) adsorbed onto the surface of fluorapatite mineral. The acidity of the water solution was varied between pH 5.4 and pH 8.4. In this pH range the infrared spectra of adsorbed ARS show that the fluorapatite surface contains precipitated calcium-ARS. The chelation of calcium strongly affects the resonance structure of the ARS molecule.
The adsorption of 1,2-dihydroxyanthraqinone-3-sulphonate (ARS) onto the surface of fluorite mineral was studied using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and Fourier transform (FT) Raman spectroscopy. The FT-Raman method proved to be more appropriate for this study when ARS was adsorbed from alkaline solution. At pH 6 both DRIFT and Raman spectra indicate non-precipitated ARS on the fluorite surface. At higher pH Raman spectra indicate ARS to be attached to the fluorite surface through the quinoid group at the 9-position and the α-phenolic oxygen.
Rapid hydration reactions of several calcium minerals are studied using Fourier transform (FT) Raman and infrared (IR) spectroscopy. Oleate adsorption over aqueous synthetic fluorite, calcite and gypsum (pH 9) is investigated and adsorption mechanisms are discussed.
The bonding of mandelic acid enantiomers has been studied on benzene-leucine, dinitrobenzene-leucine and dinitrobenzene-phenylalanine type chiral stationary phases connected to zeolite A supports. The π-donor, π-acceptor and H-bonding interactions responsible for diastereomer pair formations can be studied under quasi in situ chromatographic conditions by Fourier transform Raman and surface enhanced Raman spectroscopic techniques. Structural differences between diastereomer pairs result in observable spectral differences at a phase load of approx. 50%. It was shown that the decreasing π-acceptor character of the phase is associated with its increasing capability of H-bond formation. Correlating spectral data to chromatographic results it can be concluded that, in addition to H-bonding as well as to π-donor-π-acceptor interactions, steric hindrances due to bulky moieties of either the stationary phase or the analyte molecules are of importance in successful separations.
The adsorption mechanism of poly(1-vinyl-2-pyrrolidone) (PVP) and azelaic acid on synthetic γ-aluminium oxide surfaces was investigated using FT-IR spectroscopy. It was found that PVP adsorption from both aqueous and ethylene glycol (EG) solutions, was negligible, but the presence of the dicarboxylic acid enhances the adsorption of the PVP, due to a hydrophobic interaction between the carbon chains of the polymer and the dicarboxylic acid. The carbon chain of the adsorbed dicarboxylic acid is lateral to the surface and attached to it by both carboxylic groups. The simultaneous adsorption of PVP and azelaic acid was studied as a function of time, pH, solvent and ionic strength of the suspension in order to establish a more detailed surface complexation model. Three main surface complexes were found on the surface of the γ-alumina at low pH in aqueous as well as in EG solutions, while at high pH one of them namely the outer-sphere complex dominates.
Temporal variations in the iron isotopic composition, δ56Fe between − 0.13‰ and 0.31‰, have been measured in the suspended fraction in a Boreal river. The major mechanism behind these variations is temporal mixing between two types of particles–colloids, Fe-oxyhydroxides and Fe–C colloids. Data in this study indicate that these two types of colloids have different Fe-isotope composition. The Fe–C colloid has a negative δ56Fe value whereas the Fe-oxyhydroxide colloid is enriched in 56Fe. These two types of colloidal matter have different hydrogeochemical origin. The Fe–C colloid reaches the river during storm events when the upper sections of the soil profile (O and E horizons) are flooded by a rising water table. Colloidal Fe-oxyhydroxides reach the river via inflow and subsequent oxidation of groundwater enriched in dissolved Fe(II).
O,O′-Dipropyldithiophosphate and O,O′-dibutyldithiophosphate (Dtph) cadmium(II) complexes were prepared and studied by means of heteronuclear 31P, 113Cd, 31C CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. Linear-chain polynuclear structures have been established for both cadmium(II) complexes, in which each pair of equivalent dithiophosphate groups, playing the same bridging structural function, asymmetrically links the neighbouring cadmium atoms. One remarkable structural feature of the synthesised cadmium(II) compounds is defined by the alternation of two types of conformationally different (‘chair'-‘saddle') eight-membered rings [Cd2S4P2] in the polymeric chains. Therefore, in both 31P NMR and XRD data, the bridging dithiophosphate ligands exhibit structural inequivalence in pairs. The structural states of both Dtph ligands and cadmium atoms have been characterised by the 31P and 113Cd chemical shift tensors, which display a profound axially symmetric and mainly rhombic characters, respectively. All experimental 31P resonances were assigned to the phosphorus structural sites in both resolved structures.
The structures and spectroscopic properties of mononuclear and binuclear mercury(II) and copper(II) complexes with four dithiocarbamate ligands R 2NC(S)S- (R = CH3, C2H5, or iso-C3H7; R2 = (CH2)6) were studied by solid-state 13C and 15N CP/MAS NMR and EPR spectroscopy. Mercury(II) N,N-cyclohexamethylenedithiocarbamate [Hg 2{S2CN(CH2)6}4] was obtained and characterized in detail by X-ray diffraction analysis at 299 K. The binuclear molecule of the complex is centrosymmetric; the central tricyclic fragment [Hg2S4C2] is in the chair conformation. In the 13C and 15N NMR spectra, the signals were assigned to the dithiocarbamate ligands with different structural functions: bidentate chelating and combined (both chelating and bridging) ones. The differences between the isotropic 15N chemical shifts for the dialkyldithiocarbamate ligands were interpreted in terms of combination of the mesomeric effect of the =NC(S)S-groups and the inductive effect of the alkyl substituents. According to the EPR data, copper(II) in magnetically diluted systems is mainly found in heterobinuclear molecules [CuHg(S2CNR 2)4] and the geometry of the chromophores [CuS 5] approximates to a tetragonal pyramid.
31P NMR signals for the terminal and bridging ligands of the complexes were differentiated. The experimental NMR spectra show 31P-111,113Cd and 113Cd-31 P spin-spin couplings only for the terminal ligands. The chemical shift anisotropy δ and the asymmetry parameter η were calculated for 31P and 113Cd NMR signals. It was found that the 31P chemical shifts for the terminal and bridging dithiophosphato groups differ in anisotropy character.
Dithiophosphate zinc(II) complexes with eight different O,O′-dialkyldithiophosphate ligands have been prepared in solid/liquid states and as surface complexes on a synthetic sphalerite, and studied by means of 31P NMR spectroscopy. All 31P resonances, corresponding to dithiophosphate ligands with different structural functions (i.e. terminal chelating or bridging between two metal atoms in bi- and tetranuclear complexes), have been assigned on the basis of comparative analyses of chemical shift data for solid complexes, their melts and chloroform solutions at various concentrations. The bridging coordination of O,O′-dialkyldithiophosphate ligands by the two neighbouring zinc(II) atoms was established in the case of zinc(II) complexes formed at the surface of the synthetic sphalerite. In addition, novel molecular and crystal structures of the binuclear O,O′-di-cyclo-hexyldithiophosphate zinc(II) complex have been resolved by single-crystal X-ray diffraction data analysis, and useful correlations with 31P NMR data for this complex were obtained.
Crystalline thallium(I) alkylxanthate complexes [Tl{S(S)COR}]n (R = C2H5, i-C3H7, i-C 4H9, s-C4H9, and C5H 11) and isotope-substituted heteropolynuclear Cu(II)Tl(I) complexes [63(65)CuTl6(S2COR)8] (R= i-C 4H9 and C5H11) were obtained and studied by ESR and high-resolution solid-state 13C CP/MAS NMR spectroscopy. According to the 13C NMR data, polynuclear thallium(I) complexes contain structurally equivalent alkylxanthate ligands. The ESR study revealed the Jahn-Teller dynamic effect in Cu(II)Tl(I) complexes; the nuclei of six Tl atoms are involved in the hyperfine interaction
Alkylxanthate complexes of the general formula [M{S(S)COR}2] (M = Ni, 63Cu, and 65Cu; R = C2H5, i-C3H7, i-C4H9, s-C4H9, and C5H11) were synthesized and studied by EPR and high-resolution solid-state 13C CP/MAS NMR. In the copper(II) complexes stabilized in the matrix of nickel(II) compounds, square planar chromophores [CuS4] are characterized by rhombic distortion (EPR data). Experimental EPR spectra were simulated at the second order of perturbation theory. Nickel(II) complexes were characterized by 13C NMR spectra. In all cases, the -OC(S)S- groups were found to exhibit intramolecular structural equivalence.
A comparative study of polynuclear thallium complexes with dialkyldithiocarbamates [Tl2{S2CNR2}2]n (R = CH3, i-C3H7, C4H9, and i-C4H9; R2 = (CH2)6) was performed by solid-state 13C and 15N CP/MAS NMR spectroscopy. The dithiocarbamate groups were found to be structurally equivalent in the complexes studied. An increase in the positive inductive effect of alkyl substituents at the N atom increased 15N chemical shifts as a result of a combination of positive inductive effect of the alkyl substituents and the mesomeric effect of=NC(S)S-groups. The first representative of thallium(I) complexes with a cyclic dithiocarbamate ligand [Tl2{S2CN(CH2)6}2]n was obtained. Its molecular structure was determined from X-ray diffraction data. The β-form of the isotope-substituted complex [63/65CuTl2{S2CN(CH2)6}4] was obtained and examined by EPR spectroscopy. The EPR spectra were modeled at the second order of the perturbation theory. The spin density at the thallium atoms was calculated and its distribution over the AOs of thallium was determined.
Crystal adducts of diethyldithiocarbamate complexes of zinc(II) and copper(II) with piperidine (Pip) were synthesized, and their solvated forms with the outer-sphere molecules of benzene, pyridine (Py), and morpholine (Mf) were obtained. Adducts with composition [M(Pip)(Edtc)2] · L (L = Py, Mf) were shown to be able, in principle, to give solvated isomers [M(L)(Edtc)2] · Pip with the Pip molecule arranged in the outer sphere. The composition, structure, and properties of the obtained adducts were studied by EPR, high-resolution solid-state 13C, 15N NMR spectroscopy. Solvation of all three adducts with Pip, Mf, and Py was found to result in a substantial increase in the contribution of the trigonal-bipyramidal component to the geometry of a copper coordination pentahedron. In addition, for adducts with Mf and Py, a structural unification of two isomeric forms was observed at the molecular level to yield a qualitatively new (rather than intermediate) state. It was shown that in all solvated forms of the copper(II) adducts, the metal polyhedron is mainly a trigonal bipyramid, while the square-pyramidal contribution is insignificant. Results of (13C, 15N) NMR studies revealed a structural inequivalence of the Edtc-ligands in the zinc adducts under investigation.