Preparation and studies of new crystals in the K3H(SO4)2-(NH4)3H(SO4)2-H2O system

To elucidate the effect of isomorphic substitution on the kinetics of phase transitions, single crystals of (K _x (NH₄)_1?x ) _m H _n (SO₄)_{(m + n)/2} · yH₂O solid solutions are grown from the K₃H(SO₄)₂-(NH₄)₃H(SO₄)₂-H₂O system, whose end members are known to undergo superprotonic phase transitions of fundamentally different kinetics. The chemical composition of the single crystals grown is determined by energy dispersive X-ray microanalysis. The thermal and optical behavior of (K,NH₄)₉H₇(SO₄)₈ · H₂O single crystals is studied in the temperature range 295–420 K and the crystal structure at 295 K is determined. A comparison of the results of the studies with data for crystal K₉H₇(SO₄)₈ · H₂O published earlier shows that the substitution of ammonium for potassium atoms lowers the temperature of the structural phase transition by 8 K.     

Refractive indices of (NH4)2SO4 crystals under uniaxial pressure

Crystallography Reports - The effect of uniaxial pressure σ m ≤ 200 bar on the spectral (300–800 nm) and temperature (300–77 K) dependences of the refractive indices...     

X-Ray Radiography Investigations of Solid Solutions with Limited Miscibility in K2SO4-(NH4)2SO4-H2O System

The measurements of crystal lattice parameters (a, b, c) were conducted and the volumes (v) and densities (∂) of solid solutions of (K, NH₄)₂SO₄ were calculated. It was established that in the system K₂SO₄-(NH₄)₂SO₄-H₂O at 25 °C mixed crystals with limited miscibility were formed. The gap in the continuity of solid solutions occurred in a very narrow range of concentrations of (NH₄)₂SO₄ in mixed crystals, namely from 69.5 to 72.5%. In order to get the confirmation of the above, the detailed equilibrium investigations nearby the peritonic point (the concentration of K₂SO₄ −3.32%, the concentration of (NH₄)₂SO₄ −38.66%) were carried out.     

The Characteristics of the Mixed Crystals of the K2SO4-(NH4)2SO4-H2O System at 298 K

Equilibrium studies of the K₂SO₄-(NH₄)₂SO₄-H₂O system at 298 K have been conducted. The isotherm of solubility and the curve of distribution have been mathematically described. The parameters of the crystal lattice and the enthalpy of crystallization of the [K_x(NH₄)_1-x]₂SO₄ solid solutions as a function of their composition have been presented.     

The nature of spontaneous twisting of (NH4)2SO4 crystals at the curie point

Spontaneous twisting of (NH₄)₂SO₄ crystals at the phase transition from the paraelectric phase Pnam to the ferroelectric phase Pna2 (T _C = 223 K) was studied using the method of low-frequency torsion pendulum. It is shown that the macroscopic twisting of samples is caused by the rearrangement of ferroelastic twins with the {011} and {031} twinning planes existing in both the paraelectric and ferroelectric phases. A model interpreting the effect of the spontaneous twisting below the ferroelectric Curie point is proposed.     

Crystal structure of NH3(CH2)2NH3(BiI4)2·4H2O

The ethylenediammonium bis tetraiodobismuthate(III) tetrahydrate salt is monoclinic with the following unit cell dimensions:a=7.476(3)Å,b=13.194(3)Å,c=13.916(9)Å, β=95.22(6)°, space groupP2₁ lc withZ=2. The structure consists of disordered ethylenediammonium cations, water molecules and polynuclear anions in which slightly distored [BiI₆]^3? octahedra sharingcis edges are interconnected into chains. The [BiI₄]^? anions are connected through O(W2)?H...I hydrogen bonds, so that infinite two dimensional chains parallel to thea axis with anionic period [BiI₄(H₂O)]^? are formed in the structure. These chains are themselves interconnected by means of the O?H...I and N...O(I) bonds originating respectively from the water molecules and the ethylenediammonium entities, forming a three-dimensional network.     

Modulated crystal structures of phases VII and V in (NH4)3H(SO4)2. Neutron Laue diffraction

A study of the crystal structure of the phases VII and V of (NH₄)₃H(SO₄)₂ by mean of neutron Laue diffraction was carried out at temperatures from 5 to 300 K. It is found that the crystal structures of phases VII and V are incommensurately modulated with different periods, and that the phase transition from phase VII to phase V is of first order.     

Molecular structure of trans-[Co(NH3)4(NH2CH3)Cl](ClO4)2

The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I>2(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH₃)₄(NH₂CH₃)Cl](ClO₄)₂ molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.     

3D-incommensurate composite structures in (Rbx(NH4)(1 − x))2SO4 crystals

Detailed structural studies of (Rb_x(NH₄)_{(1 ? x)})₂SO₄ solid solutions have been performed. It is shown that the crystals consist of incommensurate composite phases. The newly discovered composite structures differ from the traditional composite phases—in the general case, the host and guest structures of these crystals are incommensurate along all the three crystallographic axes.     

The growth of single crystals of langbeinites Rb2Cd2(SO4)3, Tl2Cd2(SO4)3, K2Co2(SO4)3, and their phase transitions

Single crystals of dicadmium dirubidium sulphate and dicadmium dithallium sulphate have been grown from non-stoichiometric aqueous solutions by various methods. Optical and thermal properties in the vicinity of their phase transitions have been studied. Polycrystalline samples of dicobalt dipotassium sulphate have been prepared using Bridgman method. Optical and specific heat measurements have shown a new phase transition at −148°C.     

Crystal Growth in Magnetic Fields (II) Crystallization of Co(NH4)2(SO4)2 · 6 H2O from Aqueous Solutions in High Magnetic Fields

The displacement rate of (110) single crystal faces of Co(NH₄)₂(SO₄)₂ · 6 H₂O has been measured in dependence on the supersaturation of aqueous solutions in the zero field and at magnetic flux densities of 7 T. The results show that in a given external field measurable effects near the equilibrium don't occur (thermostatic field effect). On the contrary a marked influence at extreme relative supersaturations can be observed (kinetic field effect).     

Non-crystallographic symmetries in the superstructure of (NH4)2ZnCl4

The modulation vector turned out to be equal 1/4. The lattice constants of the orthorhombic superstructure are determined: a = 12.6197(16) Å, b = 7.2107(81) Å, c = 4 × 9.2746(15) Å. The two of the four absences rules are interpreted as corresponding to the non-crystallographic symmetries: The space group P 2₁cn is determined on the basis of the single crystal X-ray pictures taking into account the experimental evidence of pyroelectricity in (NH₄)₂ZnCl₄.     

[Pd(NH3)4]2+负载氢基钛酸盐纳米管的制备及表征

以水热法制备的氢基钛酸盐纳米管(H-TNT)为基体,利用其离子交换性能在碱性条件下制备了[Pd(NH3)4]2+负载的氢基钛酸盐纳米管.采用ICAP、XRD、TEM、DRS、XPS等手段对材料进行了表征,研究了[Pd(NH3)4]2+的浓度和溶液的pH值对氢基钛酸盐纳米管离子交换性能的影响以及交换后样品的晶型、微观形貌、光学性能以及化学组成.结果表明:[Pd(NH3)4]2+负载在H-TNT表面,相互之间以Pd-O键作用.[Pd(NH3)4]2+负载之后,样品的晶型和管状形貌都没有变化,但是在400 ～ 600 nm范围对可见光有明显吸收.溶液浓度和pH值均对离子交换性能有影响,当[Pd(NH3)4]2+浓度较小,溶液中Pd与H-TNT的质量比较小时,[Pd(NH3)4]2+在9≤pH≤12的范围内能够全部负载到H-TNT上;当[Pd(NH3)4]2+浓度较大,溶液中Pd与H-TNT的质量比较大时,增大浓度和pH值均有利于[Pd(NH3)4]2+负载比例的提高,但pH≥10时,[Pd(NH3)4]2+的负载量却趋于饱和.     

EPR and pulsed NMR study of (NH4)2ZnBr4:Mn2+

The EPR and pulsed NMR measurements of (NH₄)₂ZnBr₄:Mn²⁺ have been carried out in the temperature range 110–473 K and 83–284 K, respectively. EPR spectra from three different paramagnetic entities have been observed. Intensity changes of certain lines in the EPR spectrum observed at ≈ 430 K indicate the occurrence of a phase transition. Another phase transition at ≈ 235 K is indicated as a change of slope in the T₁ vs 1/T curve.     

Crystal structure of pentakis ethylenediammonium bis undecachlorodiantimonate(III) tetrahydrate, (NH3(CH2)2NH3)5(Sb2Cl11)2·4H2O

The pentakis ethylenediammonium bis undecachlorodiantimonate(III) tetrahydrate salt is monoclinic with the following unit cell dimensions:a=16.271(5) Å,b=13.004(4) Å,c=13.932(4) Å, β=111.72(2)°, space groupP2₁/c withZ=2. The structure was solved by Patterson methods and refined to a finalR value of 0.023 for 4435 reflections withF ₀>4σ(F ₀). The structure shows a layer arrangement perpendicular to thea axis: planes of the [Sb₂Cl₁₁]⁵⁻ bioctahedra alternate with planes of [NH₃(CH₂)₂NH₃]²⁺ dications. The [Sb₂Cl₁₁]⁵⁻ bioctahedra are connected through O−H...Cl hydrogen bonds, such that infinite chains of composition [Sb₂Cl₁₁(H₂O]_n ⁵ⁿ⁻ are formed in the structure, parallel to the twofold axis. These chains are themselves interconnected by means of N−H...Cl and O−H...Cl bonds originating from the [NH₃(CH₂)₂NH₃]²⁺ entities and the water molecules, respectively, and form a threedimensional network.     

Thermal induced structural properties of silver(I) sulphate (Ag2SO4)

The crystal structures of silver(I) sulphate, Ag₂SO₄, have been investigated as a function of temperature. A main feature is the phase transition from the low‐temperature ordered phase, F ddd, to the high‐temperature disordered phase, . In particular, the high‐temperature structure is solved from single crystal synchrotron X‐ray measurements. In this phase the title compound undergoes a colossal (anisotropic) thermal expansion of . This is presumably owing to a high anisotropic vibration state of one of the two crystallographically independent Ag‐atoms. Simultaneously occurring high ionic conductivity may be associated with silver ions moving along the ‐axis using a “paddle‐wheel” assisted percolative mechanism. Onset of metallic silver in the single crystals is documented, seemingly dependent on thermal pre‐history, mosaic structure and chemical synthesis. Possible mechanisms explaining this effect, comprising disproportionation or photo‐decomposition, are suggested.     

Surface Evolution at the Phase Transitions in (NH4)3H(SeO4)2 Crystals

Crystallography Reports - The (NH4)3H(SeO4)2 crystals in the temperature range of 296–343 K and the evolution of their surface at phase transitions have been studied by atomic force...     

Crystal Growth in Magnetic Fields (I) Crystallization of Me (NH4)2(SO4)2 · 6 H2O (Me = Zn,Cu, Ni,Fe) from Aqueous Solutions in Moderate Magnetic Fields

There are several reports in the literature concerning the study of the influence of magnetic fields on nucleation and crystal growth. Because of the partially opposite findings, the question whether the application of magnetic fields especially for mass crystallization processes may be of advantage has not been cleared yet. Therefore, the displacement rates of [110] and [001] single crystal faces of four Tutton's salts Me(NH₄)₂(SO₄)₂ · 6 H₂O (Me = Zn, Cu, Ni, Fe) from supersaturated aqueous solutions in a transversal direct magnetic field (B ≦ 1.4 T) has been measured and compared. Within the detection limit no reproducible effect was observed with Me = Zn, Cu, and Fe. A small growth acceleration occured in case of Ni(NH₄)₂(SO₄)₂ · 6 H₂O. The results which will be completed by measurements at higher magnetic flux densities, support the viewpoint that the application of magnetic fields on crystallization of diamagnetic substances from solutions offers no real advantage.