Studies on the thermal decomposition of calcium carbonate in the presence of alkali salts (Na2Co3, K2CO3 and NaCl)

Mixtures of CaCO₃ and varying amounts of Na₂CO₃, K₂CO₃ and NaCl were subjected separately to thermal analysis. DTG, DTA, TG analyses indicate that the presence of alkali salts in CaCO₃ influences its decomposition behaviour. A minimum DTA peak temperature of CaCO₃ decomposition is noticed at low concentrations of alkali salts (K₂CO₃ and Na₂CO₃); an increase in concentration increases the DTA peak temperature. However, in the case of NaCl no appreciable lowering of the DTA peak temperature of CaCO₃ decomposition is observed. Similarly, the minimum temperature at which decomposition completes is found to correspond to the concentration of 1 per cent salt (K₂CO₃ and Na₂CO₃) in CaCO₃.     

Study on the effects of flame retardants on the thermal decomposition of wood by TG–MS

The effect of three flame retardants, K₂CO₃, Na₂SiO₃·9H₂O, and Na₂B₄O₇·10H₂O on the process and composition of volatile products of the thermal degradation of wood has been investigated by the thermogravimetric (TG), differential thermogravimetry (DTG), differential thermal analysis (DTA), and the synchronous thermogravimetry–mass spectrometry (TG–MS) analysis methods. The results showed that the ion current intensity and ion peak area of m/z = 18 and 44 MS signals were increased by the flame retardants but the ion peak area of m/z = 28 MS signal was decreased (except K₂CO₃) at the meantime. What’s more, the ion current intensity and ion peak area of m/z = 60 and 68 MS signals were also decreased (except K₂CO₃), which mean that Na₂B₄O₇ can significantly enhances the dehydration and inhibits the depolymerization of wood. Although K₂CO₃ accelerates the dehydration reaction, it cannot inhibit the depolymerization reaction effectively, so the flame retardant efficiency of K₂CO₃ is decreased with the higher concentration. The catalysis of dehydration reaction of Na₂SiO₃ is the worst one.     

Gas‐phase fragmentation of metal adducts of alkali‐metal oxalate salts

Upon collisional activation, gaseous metal adducts of lithium, sodium and potassium oxalate salts undergo an expulsion of CO₂, followed by an ejection of CO to generate a product ion that retains all three metals atoms of the precursor. Spectra recorded even at very low collision energies (2 eV) showed peaks for a 44‐Da neutral fragment loss. Density functional theory calculations predicted that the ejection of CO₂ requires less energy than an expulsion of a Na⁺ and that the [Na₃CO₂]⁺ product ion formed in this way bears a planar geometry. Furthermore, spectra of [Na₃C₂O₄]⁺ and [³⁹K₃C₂O₄]⁺ recorded at higher collision energies showed additional peaks at m/z 90 and m/z 122 for the radical cations [Na₂CO₂]^+? and [K₂CO₂]^+?, respectively, which represented a loss of an M^? from the precursor ions. Moreover, [Na₃CO₂]⁺, [³⁹K₃CO₂]⁺ and [Li₃CO₂]⁺ ions also undergo a CO loss to form [M₃O]⁺. Furthermore, product‐ion spectra for [Na₃C₂O₄]⁺ and [³⁹K₃C₂O₄]⁺ recorded at low collision energies showed an unexpected peak at m/z 63 for [Na₂OH]⁺ and m/z 95 for [³⁹K₂OH]⁺, respectively. An additional peak observed at m/z 65 for [Na₂¹⁸OH] ⁺ in the spectrum recorded for [Na₃C₂O₄]⁺, after the addition of some H₂¹⁸O to the collision gas, confirmed that the [Na₂OH] ⁺ ion is formed by an ion–molecule reaction with residual water in the collision cell. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of crystalline yttrium oxycarbonate in a single phase

Crystalline yttrium oxycarbonate, Y₂O₂CO₃, was synthesized by our original flux method using the 0.476Li₂CO₃-0.270Na₂CO₃-0.254K₂CO₃ eutectic mixture at 450 °C. The oxycarbonate was characterized by X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and Fourier-transfer infrared spectroscopy (FT-IR). The Y₂O₂CO₃ prepared by the flux method was a crystalline single phase of hexagonal rare earth oxycarbonate (type-II). This is the first report on the single-phase synthesis of crystalline hexagonal type-II Y₂O₂CO₃.     

Potentiometrische säure-base-titrationen in alkalisulfatschmelzen

Using the Pt-(O₂) electrode as an indicator electrode for the O^2? concentration of a sulphate melt, potentiometric acid-base titrations have been carried out at 625°C in the eutectic Li₂SO₄-K₂SO₄-Na₂SO₄ melt. Na₂CO₃ has been used as an O^2? donor, and MoO₃, K₂Cr₂O₇, NaPO₃, Na₄P₂O₇ and V₂O₅ were used as acid species. While the equivalence point is at an acid/Na₂CO₃ molar ratio of 1:1 with MoO₃, K₂Cr₂O₇, NaPO₃ and Na₄P₂O₇, it is situated at about 0.3:1 in the system V₂O₅/Na₂CO₃.     

Specific features of the interaction of α- and γ-modifications of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> with carbonate and carbonate-chloride melts

Data on reactivities of α- and γ-Al₂O₃ finely dispersed powders in a melted carbonate eutectic (Li₂CO₃–Na₂CO₃–K₂CO₃)_eut and carbonate-chloride mixture 0.72(Li₂CO₃–Na₂CO₃–K₂CO₃)_eut–0.28NaCl were obtained. The methods of synchronous thermal and X-ray phase analyses and Raman spectroscopy confirmed that, in contrast to γ-Al₂O₃, α-Al₂O₃ does not chemically interact with the melted carbonate eutectic and carbonate-chloride mixture (Li₂CO₃–Na₂CO₃–K₂CO₃)_eut–NaCl can be recommended as a thickening agent for a carbonate fuel cell.     

Reaction of 4-Nitrophthalonitrile with Carbonate,Nitrite, and Fluoride

In DMSO and DMF at elevated temperatures, KF, KNO₂, NaNO₂, K₂CO₃, and Na₂CO₃ react with 4-nitrophthalonitrile to form 4,4′-oxybis-(phthalonitrile) and, mostly, 4-hydroxyphthalonitrile. Formation ratios depend on reaction conditions. Intermediates are discussed.     

Thermal sensitivity of poly(N-vinylpyrrolidone) solutions in water-saline media

The effect of salts on the behavior of aqueous solutions of poly(N-vinylpyrrolidone), which is known to show no thermal sensitivity in the absence of additives, has been studied. The introduction of some salts, for example, KF, KH₂PO₄, K₂CO₃, and Na₂SO₄, leads to the occurrence of phase transitions. The corresponding phase transition temperatures depend on the nature and concentration of salts. Even moderate concentrations (0.3–0.6 mol/l) of the most active salts (K₂CO₃ and Na₂SO₄) are shown to reduce the phase transition temperature to 10–20°C.     

Copper-mediated direct arylation of benzoazoles with aryl iodides

The direct arylation of 1,3-benzoazole compounds with aryl iodides is effectively promoted by CuI with use of PPh₃ and Na₂CO₃ or K₃PO₄ as ligand and base, respectively, in DMF or DMSO to produce the corresponding 2-arylated products with good yields.     

Thermal studies on oxalate complexes. II. Complexes of iron (III) and chromium (III)

The decomposition of solid K₃[Fe(C₂O₄)₃] · 2 H₂O and K₃[Cr(C₂O₄)₃] · 3 H₂O has been studied using TGA and DSC. After dehydration, the chromium compound was found to decompose by the loss of CO in two steps, the loss of CO₂ and additional CO, and finally the loss of CO₂. The final product appears to be either K₃CrO₃ or the mixed oxides of chromium and potassium. Kinetic parameters and enthalpy data are presented for these reactions. In the case of K₃[Fe(C₂O₄)₃] · 2 H₂O, dehydration is followed by the loss of CO₂ and CO, CO₂ alone, and finally CO. The final product appears to be a basic carbonate of the type K₃[FE(O)₂(CO₃)]. Kinetic and thermal data are presented for most of these decomposition reactions.     

The use of the Ta/Ta2O5 electrode as an indicator electrode in potentiometric acid-base titrations in fused KNO3

The present paper reports the potentiometric titration of four acids, NaPO₃, Na₄P₂O₇, NaH₂PO₄ and K₂HPO₄, and their mixtures with K₂CO₃ and Na₂O₂ as titrants in molten KNO₃ at 350°C, using the Ta/Ta₂O₅ electrode as an indicator electrode.     

碱金属助剂类型及前驱物对改性NiAl复合氧化物催化分解N2O活性的影响

制备了不同Ni/Al原子比的NiAl类水滑石样品,焙烧获得NiAl复合氧化物,用于N₂O分解反应,研究了NiAl复合氧化物组成对催化活性的影响。在活性较高的NiAl复合氧化物表面浸渍碱金属碳酸盐溶液,制备改性NiAl复合氧化物,考察了碱金属类型（Na、K、Cs）和钾前驱物（K₂CO₃、K₂C₂O₄、CH₃COOK、KNO₃）对改性催化剂活性的影响。用XRD、ICP-AES、FT-IR、BET、H₂-TPR、XPS技术表征了催化剂的组成结构。结果表明,Ni/Al原子比为2.7的NiAl复合氧化物催化活性较高;Na、K、Cs碳酸盐改性NiAl复合氧化物均提高了催化剂活性,其中K的助剂效应最强。钾前驱物对K改性NiAl复合氧化物的催化活性有显著影响,其中碳酸钾、醋酸钾、草酸钾的加入明显提高了改性催化剂的催化活性,而加入硝酸钾反而降低了催化剂活性。     

The Synthesis of Novel Crown Ethers. Part IV. Coumarin Derivatives of [18]crown-6 and Cation Binding from Fluorescence Spectra

4-H, 4-methyl and 4-phenyl-1-benzopyran-2-one derivatives of [18]crown-6 derivatives were synthesised from 6,7- and 7,8-dihydroxy-1-benzopyran-2-one reacting with pentaethylene glycol ditosylate in K₂CO₃/DMF/water. The products were identified by elemental analysis, EI-GC-mass spectra and ₁H-NMR spectroscopy. The Na⁺ association constants of some coumarin derivatives were determined with an ion selective electrode in water. The Na⁺ , K⁺, Ba²⁺ and Sr²⁺ binding role of such compounds were particularly observed as remarkable alterations in acetonitrile. The 1 : 1 associations constants of K⁺ and Na⁺ with some coumarin-[18]crown-6 derivatives estimated by this way in acetonitrile exhibited the utility of complexing enhanced quenching fluorescence spectra for the ion binding power of the such macrocycles.     

Rapid gelometric assay of theophylline

A simple gelometric procedure for rapid identification and determination of theophylline is described. The method is based on the observation that the addition of CuSO₄ (1%) followed by the addition of Na₂CO₃ (2%) to theophylline forms a transparent bluish green gel. The gel is then treated with Na⁺/K⁺-tartrate (4%) in 10% Na₂CO₃ to dissolve CuCO₃---Cu(OH)₂ which would percipitate in the presence of excess CuSO₄. The gel suspension is next centrifuged at 8000g and the supernatant is collected. The concentration of Cu²⁺ in the supernatant is measured spectrophotometrically at 410 nm by adding 10% NaN₃ in 0.5 sodium phosphate buffer, pH 7.0 (1:10). The decrease of absorbance at 410 nm is directly proportional to the increasing concentration of the drug in the sample (0–4 μmol). No other xanthine deriviative would form gel with CuSO₄ under the above conditions.     

Fundamentals in CO_2 capture of Na_2CO_3 under a moist condition

Capacity and kinetics of CO_2 capture of Na_2CO_3 were studied to determine the mechanism for CO_2 sequestration under ambient conditions. Bicarbonate formation of Na_2CO_3 was examined by a thermogravimetric analysis(TGA) under various CO_2 and water vapor concentrations and the accompanying structural changes of Na_2CO_3 were demonstrated by X-ray diffraction(XRD). Morphological variations were observed during the reaction of CO_2 capture through scanning electron microscope(SEM). Structural changes and morphological variations, which occurred during the course of the reaction, were then connected to the kinetic and exothermic properties of the CO_2 capture process from the XRD and SEM measurements. The results showed that the bicarbonate formation of Na_2CO_3 has two different pathways.For higher CO_2 and H_2O concentrations, the bicarbonate formation proceeded effectively. However, for lower CO_2 and H_2O concentrations, the reactions were more complicated. The formation of Na_2CO_3·H_2O from Na_2CO_3 as the first step, followed by the subsequent formation of Na_5H_3(CO_3)_4, and then the bicarbonate formation proceeds. To understand such fundamental properties in CO_2 capture of Na_2CO_3 is very important for utilization of Na_2CO_3 as a sorbent for CO_2 capture.     

Separation of 97Ru from niobium target using PEG based aqueous biphasic systems

Separation of no-carrier-added (NCA) ⁹⁷Ru from bulk niobium target has been carried out for the first time using green analytical technique, aqueous biphasic system. 50 % (w/v) polyethylene glycol (PEG)-4000, against 2 M solutions of various salts such as Na-citrate, Na-tartarate, Na-malonate, Na₂CO₃, NaHSO₃, Na₂SO₄, Na₂S₂O₃ K₂HPO₄, K₃PO₄, K₂CO₃ and 4 M KOH were employed at room temperature for the extraction of NCA ⁹⁷Ru from bulk niobium. Influence of molecular weight of PEG rich phase as well as pH of some salt rich phase (e.g., Na-tartarate) on the extraction behaviour of NCA ⁹⁷Ru into PEG rich phase was also observed. In the presence of sodium-tartarate salt solution, when volume of PEG-4000: Na-tartarate was 3:1, 91 % of NCA ⁹⁷Ru was extracted into the PEG rich phase without any contamination of niobium target. Dialysis of PEG rich phase containing NCA ⁹⁷Ru was carried out against deionised water to obtained pure NCA ⁹⁷Ru.     

Five-component reciprocal systems Na,K∥Cl,CO<Subscript>3</Subscript>,MoO<Subscript>4</Subscript>,WO<Subscript>4</Subscript> and Na,K∥F,CO<Subscript>3</Subscript>,MoO<Subscript>4</Subscript>,WO<Subscript>4</Subscript>

Five-component reciprocal systems Na,K∥Cl,CO₃,MoO₄,WO₄ and Na,K∥F,CO₃,MO₄,WO₄ have been studied by differential thermal analysis (DTA) and X-ray powder diffraction (XPD). The systems have been triangulated to phase simplexes. The main reciprocal and complex-formation reactions have been revealed. The stability of [Na,K]₂CO₃, Na₂[Mo,W]O₄, and K₂[Mo,W]O₄ binary solid solutions and the nonexistence of quintuple invariant points in the title systems have been verified.     

Thermodynamics of carbon dioxide and carbonic acid: (a) the standard enthalpies of solution of Na2CO3(s), NaHCO3(s), and CO2(g) in water at 298.15 K; (b) the standard enthalpies of formation,standard Gibbs energies of formation,and standard entropies of CO2(aq), HCO3−(aq), CO32−(aq), NaHCO3(s), Na2CO3(s), Na2CO3·H2O(s), and Na2CO3·10H2O(s)

Enthalpies of solution of CO₂(g), NaHCO₃(s), and Na₂CO₃(s) in excess NaOH solution were measured at 298.15 K by solution calorimetry. The results were reduced to standard-state processes through use of results from a preceding paper, and standard enthalpies of solution for CO₂(g), NaHCO₃(s), and Na₂CO₃(s) in water at 298.15 K were found to be: ?(4720 ± 40), (4474 ± 30), and ?(6371 ± 30) cal_th mol^?1 respectively. The results of equilibrium studies involving CO₂(g) (solubility and e.m.f. studies) were reviewed and assembled,together with entropies for related solids. Standard values of ΔH_f^o, ΔG_f^o, and S^o at 298.15 K were evaluated for CO₂(aq, non-ionized), HCO₃^?(aq), CO₃^2?(aq), NaHCO₃(s), Na₂CO₃(s), Na₂CO₃·H₂O(s), and Na₂CO₃·10H₂O(s).     

A combined method for investigating solubility and determining the composition of equilibrium solid phases saturating eutonic solutions in a NaCl-Na2SO4-Na2CO3-H2O system at 50°C

The composition of equilibrium solid phases NaCl, Na₂SO₄, Na₂CO₃ · 2Na₂SO₄ (berkeyite) and NaCl, Na₂CO₃ · H₂O, Na₂CO₃ · 2Na₂SO₄ (without preparative determination), saturating E₁ and E₂ eutonic solutions respectively, was established via nonvariant area boundary determination in a NaCl-N₂SO₄- Na₂CO₃-H₂O system at 50°C with the use of a combined method.     

Crystal Structure and Raman Spectroscopic Study of K5[CuO2][CO3]

Air and moisture sensitive K₅[CuO₂][CO₃] was prepared via the azide/nitrate route from stoichiometric mixtures of the precursors CuO, KN₃, KNO₃ and K₂CO₃. According to the single‐crystal X‐ray analysis of the crystal structure [P4/nbm, Z = 2, a = 7.4067(5), c = 8.8764(8) Å, R₁ = 0.053, 433 independent reflections] K₅[CuO₂][CO₃] represents an ordered superstructure of Na₅[NiO₂][CO₃]. The structure contains isolated [CuO₂]^3– dumbbells and CO₃^2– anions, with the latter not connected to the transition element. Raman spectroscopic measurements confirm the presence of CO₃^2– in the structure.