Growth and Thermal,Electrical, Structural Characterization of Mixed Hydrated Single Crystal

Mixed single crystal was made by mixing saturated aqueous solutions of NiSO₄ · 6H₂O and CuSO₄ · 5H₂O by volume (80:20) and the mixture was kept to form the crystals at room temperature by slow evaporation process. After some days, big pieces of greenish blue, dark colored crystals were grown. To determine the weight of NiSO₄ · 6H₂O and CuSO₄ · 5H₂O in the crystal, Ni-DMG complexiometrical and EDTA gravimetrical analysis was done respectively. From this analysis it was concluded that 5.8 molecules of water of crystallization is present in the mixed single crystal. The crystals were characterized by UV-Visible, FTIR and single crystal X-ray diffraction studies. From single crystal XRD lattice parameters have been calculated. All these structural analysis confirms formation of new single crystal. Further, DTA-TGA, dc electrical conductivity and dielectric constant studies were done from the room temperature to 400 °C.From DTA studies it was observed that 5.8 molecules of water of crystallization get dehydrated in four major steps at temperature 115 °C, 150 °C, 240 °C and 325 °C respectively corresponding to the detachment of 1 mole, 3 moles, 1 mole and 0.8 mole of water of crystallization. DC electrical conductivity and dielectric constant studies also show close agreement to the dehydration steps. The observed peaks in the conductivity verses temperature graph have been explained on the basis of release of water molecules and subsequent dissociation of these released water molecules into H⁺ and OH⁻ ions.     

Study of transition temperature through mixed crystal formation,IV

The study of homogeneous distribution coefficients in determining the transition temperatures of isomorphologically analogous components and in predicting the existences of some new unstable compounds has been carried out in detail with special references to vitriols of nickel, manganese, zinc, copper and magnesium. In the course of the investigation with NiSO₄·7H₂O as host and⁵⁴Mn as guest, the transition temperature of orthorhombic NiSO₄·7H₂O was shown to be 26.5 °C, and with orthorhombic ZnSO₄·7H₂O and MgSO₄·7H₂O as host and copper sulphate as guest, the limits of existences of orthorhombic CuSO₄·7H₂O and newly predicted CuSO₄·6H₂O were found to be 13.5° to 44 °C and 44° to 51 °C, respectively. In addition, the transition temperatures of orthorhombic MnSO₄·7H₂O (10 °C), stable NiSO₄·7H₂O (30.5±5 °C) and orthorhombic ZnSO₄·7H₂O (39 °C) were verified. The new method of approach is very simple, reproducible and easily adaptable.     

The dehydration of ZnSO4·7H2O and NiSO4·6H2O

Using differential scanning calorimetry (DSC) in combination with effluent analysis, differential thermal analysis (DTA), thermogravimetric analysis (TG) and X-ray analysis, the dehydration of ZnSO₄·7H₂O and NiSO₄·6H₂O was investigated and a few transition enthalpies were measured. The dehydration of both compounds showed a great analogy. For NiSO₄·6H₂O the α—β phase transition was studied.The dehydration scheme of both hydrates can be given as follows:

     

Zur Kenntnis der Sulfite und Sulfithydrate des Eisens und Nickels Röntgenographische,thermoanalytische, IR- und Raman-spektroskopische Untersuchungen

In den Systemen FeSO₃? H₂O und NiSO₃? H₂O konnten folgende Hydrate erhalten werden: α-FeSO₃ · 3H₂O, γ-FeSO₃ · 3H₂O, FeSO₃ · 2,5 H₂O, FeSO₃ · 2 H₂O, NiSO₃ · 6 H₂O, NiSO₃ · 3 H₂O, NiSO₃ · 2,5 H₂O und NiSO₃ · 2 H₂O. Die Gitterdaten der folgenden Hydrate wurden anhand von Einkristallmessungen bestimmt: γ-FeSO₃ · 3 H₂O: a = 965,9(1), b = 557,1(1), c = 944,7(1) pm, Z = 4, FeSO₃ · 2 H₂O (P2₁/n): a = 645,6(1), b = 863,1(1), c = 761,2(1) pm, β = 99,84(1)°, Z = 4, NiSO₃ · 3 H₂O: a = 945,0(1), b = 547,2(1), c = 932,5(1) pm, Z = 4, NiSO₃ · 2,5 H₂O (P4₁2₁2): a = b = 935,3(1), c = 1016,6(1) pm, Z = 8, NiSO₃ · 2 H₂O (P2₁/n): a = 631,4(1), b = 851,0(1), c = 744,7(1) pm, β = 98,91(1)°, Z = 4. Die IR- und Raman-Spektren sowie das Ergebnis thermoanalytischer Messungen (DTA, DTG, Röntgenheizaufnahmen) werden mitgeteilt. Die bei Sulfiten und Sulfithydraten zweiwertiger Metalle bisher beobachteten Strukturtypen werden diskutiert. Sulfites and Sulfite Hydrates of Iron and Nickel. X-ray, Thermoanalytical, I.R., and Raman Data In the systems FeSO₃? H₂O and NiSO₃? H₂O the following hydrates have been found: α-FeSO₃ · 3H₂O, γ-FeSO₃ · 3H₂O, FeSO₃ · 2,5 H₂O, FeSO₃ · 2 H₂O, NiSO₃ · 6 H₂O, NiSO₃ · 3 H₂O, NiSO₃ · 2,5 H₂O and NiSO₃ · 2 H₂O. The following crystal data have been determined by single crystal measurements: γ-FeSO₃ · 3 H₂O: a = 965,9(1), b = 557,1(1), c = 944,7(1) pm, Z = 4, FeSO₃ · 2 H₂O (P2₁/n): a = 645,6(1), b = 863,1(1), c = 761,2(1) pm, β = 99,84(1)°, Z = 4, NiSO₃ · 3 H₂O: a = 945,0(1), b = 547,2(1), c = 932,5(1) pm, Z = 4, NiSO₃ · 2,5 H₂O (P4₁2₁2): a = b = 935,3(1), c = 1016,6(1) pm, Z = 8, NiSO₃ · 2 H₂O (P2₁/n): a = 631,4(1), b = 851,0(1), c = 744,7(1) pm, β = 98,91(1)°, Z = 4. IR, Raman, and thermoanalytical (DTA, DTG, high temperature X-ray) data are presented. The structure types found for sulfites and sulfite hydrates of bivalent metals are discussed.     

Thermal dehydration of inorganic salts in water-saturated nitrogen

The thermal dehydrations of CoSO₄ · 6H₂O, NiSO₄ · 6H₂O and MnSO₄ · H₂O have been investigated by TG, DTG, and DTA in water-saturated nitrogen. The starting temperatures and the “activation energy” values for each step are reported.     

Über die Entstehung ferromagnetischer Gele und einige verwandte Erscheinungen

Zusammenfassung Durch Zerreiben von Na₂SO₄·10 H₂O, MgSO₄·7 H₂O, MnSO₄·5 H₂O, NiSO₄·7 H₂O, CoSO₄-7H₂O, ZnSO₄·7H₂O CuSO₄·5 H₂O, CdSO₄·8— H₂O, HgSO₄ und (UO₂)·SO₄·3 H₂O mit FeCl₃·6 H₂O werden ferromagnetische Gele erhalten. Durch Autoklavbehandlung dieser Gele entstehen Niederschl?ge, die in ihrem Aussehen weder H?matit noch Magnetit ?hnlich erscheinen. Es wird ein Demonstrationsversuch beschrieben, mit dem der Unterschied der magnetischen Eigenschaft von Eisenhydroxyden je nach der Herstellungsart veranschaulicht wird. Die beim Mischen von Ferro- und Ferril?sungen entstehenden Farb?nderungen werden photometrisch gemessen und diskutiert.     

The deaquation reactions of some metal salt hydrates at elevated pressures

The deaquation reactions of BaCl₂·2H₂O, BaBr₂·2H₂O and CoCl₂·6H₂0 were studied by the thermal analysis techniques of thermogravimetry, differential thermal analysis (DTA), and electrical conductivity in the pressure range from one to 170 atm. In general, the effect of pressure on the TG curves increased the T_i and T_f values and also the reaction interval, (T_t—T_i). The DTA curves exhibited splittings into multiple peaks as a result of the increased pressure. These splittings were interpreted as due to the evolution of a liquid water phase followed b     

Study of the nature of the crystallization water in some magnesium hydrates by thermal methods

The nature of the crystallization water in MgSO₄·7H₂O, Mg(NO₃)₂·6H₂O and MgCl₂·6H₂O has been studied with the nonisothermal methods of thermogravimetry (TG), derived thermogravimetry (DTG) and differential thermal analysis (DTA). Analysis of the characteristic thermogravimetric data (T _M,W _∞) and the kinetic parameters (n, E _a), together with the DTA results, with CuSO₄·5H₂O as control sample, provided evidence of the existence of coordinated water and of the nature of the anions in these hydrates. The results are confirmed by the observation of a real compensation effect. For the compensation effect, the following equation is proposed: InA=0.220E-0.8 Structures explaining the presence of the coordinated water and the nature of the anions in these hydrates are also proposed.     

铁系元素冠醚配合物的研究——V.三氯化铁与4′-溴苯并-15-冠-5固态配合物的合成和性质

本文报导了三氯化铁(水合物)与4′-溴苯并-15-冠-5(L)固态配合物的合成,对合成的新配合物,进行了元素定量分析及摩尔电导测定,并作了红外光谱、紫外光谱,热重和差热以及X-射线粉末衍射分析的性质表征。从而证明,该配合物中FeCl₃与配体L比为1:1,是溶化剂,含有结晶水的固态配合物。     

水合盐的几种脱水过程探讨

通过差热/热重联机 (DTA/TGA)和差示扫描量热法 (DSC)测定几种盐(Na2SO4·10H2O、CuSO4·5H2O、Na2S2O3·5H2O)的失水过程 ,对水合盐脱水过程几种可能的类型进行探讨。研究表明低温 (100℃以下 )水合盐脱水有两种类型 ,一种直接失去气态水 ,另一类先脱去液态水再进一步变为气态水。并从热力学上理论分析两类脱水过程的原因。     

Novel Method for Preparing NH4NiPO4·6H2O: Hydrogen Bonding Coacervate Selective Self-assembly

The single phase NH₄NiPO₄·6H₂O was synthesized by solid‐state reaction at room temperature using NiSO₄·6H₂O and (NH₄)₃PO₄·3H₂O as raw materials. The NH₄NiPO₄·6H₂O and its calcined products were characterized using X‐ray powder diffraction (XRD), thermogravimetry and differential thermal analyses (TG/DTA), Fourier transform IR (FT‐IR), ultraviolet‐visible (UV‐vis) absorption spectroscopy, and scanning electron microscopy (SEM). The results showed that the product dried at 80°C for 3 h was orthorhombic NH₄NiPO₄·6H₂O [space group Pmm2(25)], and surfactant polyethylene glycol (PEG)‐400 can direct growth of crystal NH₄NiPO₄·6H₂O. The thermal process of NH₄NiPO₄·6H₂O experienced three steps, which involve the dehydration of the five crystal water molecules at first, and then deamination, dehydration of the one crystal water, intramolecular dehydration of the protonated phosphate groups together, at last crystallization of Ni₂P₂O₇. The product of thermal decomposition at 150°C for 2 h, orthorhombic NH₄NiPO₄·H₂O, is layered compound with an interlayer distance of 0.8370 nm.     

The relationship between the structures of Cu(II) complexes and their chemical transformations

The paper reports an attempt to correlate the structures of hydrates of copper(II) sulphate with some characteristic features of the kinetics of their thermal decompositions. Non-isothermal thermogravimetric measurements were employed to obtain values of experimental activation energy and entropy for the dehydration of CuSO₄ · 5 H₂O, CuSO₄ · 3 H₂O and CuSO₄ · H₂O. The values ofE ^* andΔS ^* for the dehydration of CuSO₄ · 3 H₂O were found to be only little affected by the mode of preparation of this compound. On the other hand, the values ofE ^* andΔS ^* for the dehydration of CuSO₄ · ·H₂O are strongly dependent on whether this compound was prepared by thermal decomposition of CuSO₄ · 5 H₂O or CuSO₄ · 3 H₂O, or by crystallization from solution. As regards the crystalline hydrates of copper(II) sulphate, the greatest energetic hindrance for dehydration was observed for CuSO₄ · 3 H₂O. The experimental results are also discussed with respect to the present opinions concerning the possibilities of using thermal analyses to obtain information on the relationship between the structures and reactivities of solids.     

Kinetics and thermodynamics of thermal decomposition of NH<Subscript>4</Subscript>NiPO<Subscript>4</Subscript>·6H<Subscript>2</Subscript>O

The single phase NH₄NiPO₄·6H₂O was synthesized by solid-state reaction at room temperature using NiSO₄·6H₂O and (NH₄)₃PO₄·3H₂O as raw materials. XRD analysis showed that NH₄NiPO₄·6H₂O was a compound with orthorhombic structure. The thermal process of NH₄NiPO₄·6H₂O experienced three steps, which involves the dehydration of the five crystal water molecules at first, and then deamination, dehydration of the one crystal water, intramolecular dehydration of the protonated phosphate groups together, at last crystallization of Ni₂P₂O₇. In the DTA curve, the two endothermic peaks and an exothermic peak, respectively, corresponding to the first two steps’ mass loss of NH₄NiPO₄·6H₂O and crystallization of Ni₂P₂O₇. Based on Flynn–Wall–Ozawa equation, and Kissinger equation, the average values of the activation energies associated with the thermal decomposition of NH₄NiPO₄·6H₂O, and crystallization of Ni₂P₂O₇ were determined to be 47.81, 90.18, and 640.09 kJ mol⁻¹, respectively. Dehydration of the five crystal water molecules of NH₄NiPO₄·6H₂O, and deamination, dehydration of the crystal water of NH₄NiPO₄·H₂O, intramolecular dehydration of the protonated phosphate group from NiHPO₄ together could be multi-step reaction mechanisms. Besides, the thermodynamic parameters (ΔH ^≠, ΔG ^≠, and ΔS ^≠) of the decomposition reaction of NH₄NiPO₄·6H₂O were determined.     

Detection of the quadruple point in the CuSO4·5H2O and BaCl2·2H2O systems: effect of experimental parameters

The effects of sample mass, particle size, and furnace heating rate were studied for the detection of the quadruple point in the CuSO₄·5H₂O system using the simultaneous differential thermal analysis—electrical conductivity (DTA—EC) technique. As the sample mass decreased, both the DTA and EC peak amplitudes decreased. Increasing the furnace heating rate caused an increase in the peak splitting for the first DTA peak. In the case of particle size, an optimum size of about 80 mesh was found to give a maximum in the EC curve peak. The simultaneous DTA—EC curves for BaCl₂·2H₂O are also given.     

The dehydration of nickel sulfate

Nickel sulfate was recrystallized to obtain the 7 H₂O, β6 H₂O and various habits of α6 H₂O. Dehydration and phase transitions were studied using X-ray analysis and DSC with effluent gas analysis. NiSO₄ · 7 H₂O dehydrates spontaneously via 7 → 6β → 6α at room temperature, while the dehydration pathway of NiSO₄ α6 H₂O is 6α → 6γ → 4 → 1. The effect of time and storage on the 6α—6β phase transition was investigated.     

Study of the products of the dehydration reaction of CuSO4 · 5H2O in X-shaped and elliptic nuclei

The products of the dehydration of CuSO₄ · 5H₂O under different conditions have been studied by the methods of local X-ray diffraction analysis and EPR. It is shown that the dehydration in vacuo when X-shaped nuclei are formed proceeds through the formation of an intermediate product having a monohydrate composition and a crystalline lattice close to the initial lattice of the pentahydrate. Then the amorphization and crystallization of CuSO₄ · H₂O follows. When dehydration occurs in water vapour through ellipsoidal nuclei the structure of the trihydrate formed is oriented relative to the initial structure of CuSO₄ · 5H₂O.     

Reactions of barium chloride dihydrate in potassium halide matrices: A differential scanning calorimetry study

The deaquation of BaCl₂·2H₂O in pressed KCl, KBr, and KI disks was followed by TG and DSC at pressures ranging from one to 34 atmospheres. Resolution of the DSC peaks of the first deaquation reaction and subsequent water vaporation was not improved by use of the matrix; for the second deaquation reaction, resolution was greater in the matrix. Evidence of a ternary eutectic involving BaCl₂, KI, and H₂O, which melted at 219°C, was obtained.     

Phosphonate metal–organic frameworks used as dye removal materials from wastewaters

A very intense study class of complex porous materials, metal–organic frameworks (MOFs), composed of diverse central metallic ions attached to organic linkers, was used in this study as adsorbant materials from wastewaters. Phosphonate MOFs were prepared by the reaction of divalent inorganic salts (CoSO₄ · 7H₂O, NiSO₄ · 6H₂O, CuSO₄ · 5H₂O,) with vinyl phosphonic acid in hydrothermal conditions, obtaining cobalt, nickel, and copper vinylphosphonate (CoVP, NiVP, and CuVP). During synthesis the experimental conditions were varied in terms of time, temperature, and pH. The synthesized materials were characterized by Fourier transform infrared, thermogravimetric analysis, scanning electron microscopy, and X-ray crystallography. The efficiency of MOFs as adsorbents was investigated for diverse initial dye concentrations at different pH values and at three temperatures (25, 40, and 55°C). The synthesized materials presented good efficiency in the elimination of anionic as well as cationic type of dyes from aqueous solutions. The highest adsorption capacities were obtained working at optimum solution pH 4.2 for Acid Orange 7 and 10 for Basic Fuchsine, using 1 g/L of MOFs at room temperature (25°C). The adsorption capacities increase in the following order: CuVP < NiVP < CoVP.     

Thermal properties of sodium metasilicate hydrates

The heats of fusion and heat capacities at 298.2 K of Na₂SiO₃·5H₂O, Na₂SiO₃·6H₂O and Na₂SiO₃·9H₂O have been measured by DSC. The enthalpies and entropies of fusion increase with the water content of the hydrate and the entropy of fusion per mole of water is almost constant. The application of DSC/DTA to the analysis of metasilicate hydrate mixtures is discussed.     

The role of the cation in the oxygen isotopic exchange in crystalline sulfate salt hydrates

The oxygen isotopic exchange during dehydration and decomposition of five sulfate salt hydrates (CoSO₄·6H₂O, NiSO₄·7H₂O, ZnSO₄·7H₂O, CaSO₄·2H₂O, Li₂SO₄·H₂O) was studied in detail by temperature programmed desorption mass spectrometry (TPD-MS) in a supersonic molecular beam (SMB) inlet mode. Crystals of the ¹⁸O-enriched salts were grown and the detailed desorption steps of the various gaseous products released during dehydration and decomposition of these compounds were recorded. The desorption patterns confirmed the known characteristic stepwise dehydration of these salts, where regardless of the crystalline structure and composition, in all the salts (excluding the Li and Ca sulfates) a major group of n ? 1 loosely bounded water of crystallization molecules (out of total of n molecules in the fully hydrated form) are released at adjacent temperatures in a typical low temperature range (<200 °C), while the last, most strongly bounded water molecule, consistently desorbs at relatively higher temperatures (240 < T < 440 °C). Interestingly, it is established that the oxygen isotopic exchange occurs exclusively between that latter, most strongly bound water molecule, and the salt anion. Remarkably, the results point out that the exchange process is mostly of solid-solid nature. Finally, the results point out that the probability of the isotopic exchange increases with the increment in the desorption temperature of the last dehydration step, i.e. with the bond strength in the monohydrate, between the last water molecule of crystallization and the cation.