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Institute
Chemische Transportreaktionen weisen ein gemeinsames Merkmal auf: In Gegenwart eines gasförmigen Reaktionspartners, des Transportmittels, wird eine feste oder flüssige Komponente verflüchtigt. An anderer Stelle scheidet sie sich meist in Form gut ausgebildeter Kristalle wieder ab. So ist der Chemische Transport z. B. für den Festkörperchemiker ein unentbehrliches Verfahren zur Herstellung reiner, gut kristallisierter Feststoffe. Als umfassendes Handbuch behandelt dieses Werk die vielseitigen Aspekte von chemischen Transportreaktionen: Von der Grundlagenforschung bis hin zur praktischen Bedeutung, beispielsweise für die Funktionsweise von Halogenlampen.
Since their first recognition in mineral forming processes
some 150 years ago chemical vapor transport reactions (CVTR) have attracted continuous scientific interest. Due to the pioneering work of Harald Schäfer quantitative understanding and exploitation of transport reactions for crystal growth, synthesis, investigation of high-temperature gas species, and thermodynamic studies have become possible. Renewed interest in CVT is triggered by the demand of material sciences for novel compounds with tailor-made physical properties and by the need for efficient recycling strategies for various metals from industrial waste.
Chemical Vapour Transport of Bismuth and Antimony Chalcogenides M2Q3 (M = Sb, Bi, Q = Se, Te)
(2010)
Thermodynamic modelling of the ternary systems M/Q/I (M = Sb, Bi, Q = Se, Te) indicated solid-gas equilibria suitable for chemical vapour transport of bismuth and antimony chalcogenides. The predictions of the modelling were confirmed by transport experiments on a transport balance. The optimum transport conditions using iodine as transport agent were determined for all systems to: ϑsource = 500 °C and ϑsink = 450 °C. For ΔT > 50 K the sequential transport of chalcogenide iodides MQI followed by M2Q3 occurs. Thermodynamic standard data of the gas species SbI(g) were concluded from equilibrium calculations: ΔH0f,298(SbI(g)) = 106 ± 3 kJ·mol–1; S0298(SbI(g)) = 255 ± 3 J·mol–1·K–1; Cp(SbI(g)) = 37 ± 1 J·mol–1·K–1
The term chemical vapor transport (CVT) summarizes a variety of reactions that show one common feature: a condensed phase, typically a metallic or salt like solid, is volatilized in the presence of a gaseous reactant, the so-called transport agent, and deposits elsewhere, usually in the form of crystals. The deposition will take place if the site of volatilization and the site of crystallization have different temperatures. In many cases, chemical vapor transport is associated with a purification effect. CVT-reactions of elements, oxides, sulfides, selenides, tellurides, phosphates, sulfates, halides, oxide halides, phosphides, arsenides, intermetallics, and so on, are known.
A variety of processes of crystal growth proceeds via the gas phase. If the initial solid material is volatilized in a heterogeneous reaction under presence of a gaseous reactant, the transport agent, the term Chemical Vapor Transport Reaction (CVT) is applied. Crystallization processes by CVT are known for both elements, intermetallics, binary and complex oxides, halides, chalcogenides, and pnictides. Even if the formation of volatile halides is a common feature of almost all vapor transport reactions, significant differences are there concerning the choice of a suitable transport agent depending on the nature of the initial solid phase. Actually, the appropriateness of transport agents for the respective transport reaction can be described in a thermodynamic way. Besides some basic principles for systematic evaluation more practical recommendations for suitable experimental conditions are given for CVT of different classes of inorganic materials.
Chemische Transportreaktionen weisen ein gemeinsames Merkmal auf: In Gegenwart eines gasförmigen Reaktionspartners, des Transportmittels, wird eine feste oder flüssige Komponente verflüchtigt. An anderer Stelle scheidet sie sich meist in Form gut ausgebildeter Kristalle wieder ab. So ist der Chemische Transport z. B. für den Festkörperchemiker ein unentbehrliches Verfahren zur Herstellung reiner, gut kristallisierter Feststoffe.
Als umfassendes Handbuch behandelt dieses Werk die vielseitigen Aspekte von Chemischen Transportreaktionen: Von der Grundlagenforschung bis hin zur praktischen Bedeutung, beispielsweise für die Funktionsweise von Halogenlampen.
This comprehensive handbook covers the diverse aspects of chemical vapor transport reactions from basic research to important practical applications. The book begins with an overview of models for chemical vapor transport reactions and then proceeds to treat the specific chemical transport reactions for the elements, halides, oxides, sulfides, selenides, tellurides, pnictides, among others. Aspects of transport from intermetallic phases, the stability of gas particles, thermodynamic data, modeling software and laboratory techniques are also covered. Selected experiments using chemical vapor transport reactions round out the work, making this book a useful reference for researchers and instructors in solid state and inorganic chemistry.
This comprehensive handbook covers the diverse aspects of chemical vapor transport reactions from basic research to important practical applications. The book begins with an overview of models for chemical vapor transport reactions and then proceeds to treat the specific chemical transport reactions for the elements, halides, oxides, sulfides, selenides, tellurides, pnictides, among others. Aspects of transport from intermetallic phases, the stability of gas particles, thermodynamic data, modeling software and laboratory techniques are also covered. Selected experiments using chemical vapor transport reactions round out the work, making this book a useful reference for researchers and instructors in solid state and inorganic chemistry.
Fibrous phosphorus is one of the known crystalline allotropes under standard pressure conditions. It has been predicted prior to its successful synthesis and structural characterization. The allotrope consists of parallel, tubular double strands of phosphorus, in contrast to the violet form of Hittorf's phosphorus, where the same strands are arranged in a perpendicular orientation towards each other. This structural similarity results in an almost identical energetic stability leading to a somehow problematic realization of single-phase materials. We herein report on the successful synthesis route to single phase fibrous phosphorus and the in situ characterization of its formation via the gas phase applying CuCl2 as a mineralizer. The sublimation pressure of fibrous phosphorus is slightly lower than the one of the black allotrope. This behavior indicates thermodynamic stability of fibrous phosphorus.
[Cd3Cu]CuP10 is the first representative of a class of compounds featuring polyphosphidic adamantine-analogous [P10] units, which tend to be fragmented and polymerized to [P6] rings and tubular [P26] units in the solid state. A new polyphosphide with nominal composition Cd15Cu10P46 results, featuring isolated and polymerized polyanions. Thermoanalytic experiments and phase analytic measurements substantiated the consecutive loss of P4 and Cd of the starting material via different intermediate steps. After P4 loss, the new polyphosphide occurred followed by various binary copper phosphides to the final product Cu3P.
The 1-butyl-3-methylimidazolium halide ionic liquids are stable up to temperatures of 246(1) °C ([BMIm]Cl), 260(1) °C ([BMIm]Br), and 238(1) °C ([BMIm]I). The thermal decomposition proceeds in thermogravimetric measurements with a total mass loss of 100%. Using evolved gas analysis (EGA) a complete degradation of [BMIm]X ionic liquids under formation of characteristic fragments CH3+, NHn+, C4Hn+, and CH3X+ (X = Cl, Br, I) has been observed. [BMIm]Cl shows enantiotropic polymorphism with a phase transition temperature at 30(1) °C, and melts at 74(1) °C (ΔHfus = 18 ± 0.5 kJ mol−1). Spontaneous e-crystallization and reversible phase transition have been found for cooling of the substance.[BMIm]Br melts at 78(1) °C (ΔHfus = 29 ± 0.5 kJ mol−1). The re-crystallization fails and thus a glassy solid is formed. The glass transition temperature is about −65 °C, the cold crystallization occurs between −30 and −20 °C. The application of both homogeneous and heterogeneous nucleation agents does not interfere the glassy state.
[BMIm]I undergo solidification without crystallization. The melting effect for the amorphous substance arise at −70(5) °C with ΔHfus = 0.4 ± 0.2 kJ mol−1.
Development of salt hydrate eutectics as latent heat storage for air conditioning and cooling
(2014)
Sustainable air conditioning systems require heat reservoirs that operate between 4 and 20 ◦C. A systematic search for binary and ternary eutectics of inorganic salts and salt hydrates with melting temperatures in this temperature regime and with high enthalpies of fusion has been performed by means of differential scanning calorimetry (DSC). Promising results were obtained for the pseudo-ternary system Zn(NO3)2·6H2O, Mn(NO3)2·4H2O, and KNO3 with the melting temperature range 18–21 ◦C and the enthalpy of fusion of about 110 kJ kg−1. Suitable nucleating and thickening agents have been found and tested to prevent the mixture from supercooling and phase separation.
Phase formation, stability, crystal and electronic structures of IrPTe are investigated from experiment and quantum chemical calculations. The phase formation is studied from thermodynamic data and CalPhaD modeling. Applying a high-temperature gas-balance a formation pathway for IrPTe is studied from the elements and the binary parent compounds IrTe2 and IrP2. The obtained paracostibite (CoSbS) type structure contains rarely occurring heteroatomic P-Te dumbbells. The stability of IrPTe and the found structure is studied from DFT calculations with respect to the elements, IrTe2 and IrP2, and possible polymorphs. Probable metastable modifications with XY dumbbells (as known for isoelectronic compounds like CoAsS) are obtained from systematic DFT modelling. Phase transitions are predicted form the equation of states (EOS). According to its electronic band structure IrPTe is predicted as small gap (Eg = 0.5 eV) semiconductor.
The thermochemical behavior of 1-ethyl-3-methylimidazolium [EMIm] halides (Cl, Br and I) has been investigated for their crystalline and liquid states in the temperature range from −90 °C to 600 °C using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The temperatures and enthalpies of phase transitions have been determined: Tfus = 86(1) °C, ΔHfus = 14.2(0.7) kJ mol−1 ([EMIm]Cl); Tfus = 67(1) °C, ΔHfus = 19.3(0.7) kJ mol−1 ([EMIm]Br); and Tfus = 74(1) °C, ΔHfus = 16.9(0.6) kJ mol−1 ([EMIm]I). The decomposition temperatures, determined by onset of DTG at 1 K min−1 are 233(5) °C ([EMIm]Cl), 246(5) °C ([EMIm]Br), and 249(5) °C ([EMIm]I). The maximum operation temperature (MOT) has been estimated based on dynamic TGA for an operation time of 24 h: 132 °C ([EMIm]Cl), 149 °C ([EMIm]Br), 139 °C ([EMIm]I) and 8000 h: 76 °C ([EMIm]Cl), 90 °C ([EMIm]Br), 77 °C ([EMIm]I). The decomposition products of the investigated ionic liquids (ILs) after heating experiments were identified by means of TGA complemented with mass spectrometry (MS), for establishment of the mechanism of thermal decomposition of the ILs. Complete degradation of [EMIm]X ionic liquids occurs under formation of characteristic molecule fragments CH3+, NH+, and X+, CH3X+, C2H5X+ (X = Cl, Br, I).
The reaction of antimony and selenium in the Lewis-acidic ionic liquid 1-butyl-3-methyl-imidazolium tetrachloridoaluminate, [BMIm]Cl·4.7AlCl3, yielded dark-red crystals of [Sb2Se2]AlCl4. The formation starts above 160 °C; at about 190 °C, irreversible decomposition takes place. The compound crystallizes in the triclinic space group Pequation image with a = 919.39(2) pm, b = 1137.92(3) pm, c = 1152.30(3) pm, α = 68.047(1)°, β = 78.115(1)°, γ = 72.530(1)°, and Z = 4. The structure is similar to that of [Sb2Te2]AlCl4 but has only half the number of crystallographically independent atoms. Polycationic chains 1∞[Sb2Se2]+ form a pseudo-hexagonal arrangement along [01-1], which is interlaced by tetrahedral AlCl4– groups. The catena-heteropolycation 1∞[Sb2Se2]+ is a sequence of three different four-membered [Sb2Se2] rings. The chemical bonding scheme, established from the topological analysis of the real-space bonding indicator ELI-D, includes significantly polar covalent bonding in four-member rings within the polycation. The rings are connected into an infinite chain by homonuclear non-polar Sb–Sb bonds and highly polar Sb–Se bonds. Half of the selenium atoms are three-bonded.
The synthesis of the phosphide telluride Zr2+xPTe2 was accomplished by a solid-state reaction from the elements. Le Bail refinements of the as synthesized crystalline powders as well as the thermal decomposition of Zr2PTe2 along the homogeneity range Zr2+xPTe2 under the release of P4(g) and Te2(g) evidences a maximum zirconium content according to the composition Zr2.5PTe2. The thermal decomposition product of Zr2.5PTe2 undergoes a phase
transformation to “Zr2PTe” adopting the structure motive of the binary phases ZrTe and ZrTe2. The new phase “Zr2PTe” has a wide homogeneity range Zr2–xP1–yTe1+y tolerating a deficit in the cation position and a mixed occupation of the anions. The composition of the crystalline decomposition product was determined to Zr1.95P0.84Te1.16 by Rietveld refinement and by analysing the elemental composition with ICP-OES. Zr1.95P0.84Te1.16 crystallizes in hexagonal space group P63/mmc (no. 194) with lattice constants: a = 3.8726(1) Å and c = 13.008(1) Å.
Selected allotropes of phosphorus are investigated
by different levels of density functional theory
(DFT) calculations to evaluate the relative stability orders with a special focus on the role of van der Waals interactions.Phosphorus is an excellent reference system with a large number of allotropes. Starting from low-dimensional molecular (0D, white P) and polymer structures (1D, P nanorods) to layered (2D, black P) and tubular structures (2D and 3D, crystalline forms of red P), covalent structure motifs are interconnected by van der Waals interactions. They are a key factor for the correct energetic description of all P allotropes. A comparative study is carried out within the local density approximation (LDA) and the generalized gradient approximation (GGA), with and without implementation of a dispersion correction by Grimme (GGA-D2). Our intention is to achieve a reasonable agreement of our calculations with experimental data, the plausibility of energy values, and the treatment of long-range interactions. The effect of van der Waals interactions is exemplified for the interlayer distances of black phosphorous and its electronic structure.
Phosphorus displays fascinating structural diversity and the discovery of new modifications continues to attract attention. In this work, a complete stability range of known and novel crystalline allotropes of phosphorus is described for the first time. This includes recently discovered tubular modifications and the prediction of not-yet-known crystal structures of [P12] nanorods and not-yet-isolated [P14] nanorods. Despite significant structural differences, all P allotropes consist of covalent substructures, which are held together by van der Waals interactions. Their correct reproduction by ab initio calculations is a core issue of current research. While some predictions with the established DFT functionals GGA and LDA differ significantly from experimental data in the description of the P allotropes, consistently excellent agreement with the GGA-D2 approach is used to predict the solid structures of the P nanorods.
Cd4Cu7As, the first representative of a fully ordered, orthorhombically distorted MgCu2 Laves phase
(2012)
The ternary Laves phase Cd4Cu7As is the first intermetallic compound in the system Cu–Cd–As and a representative of a new substitution variant for Laves phases. It crystallizes orthorhombically in the space group Pnnm (No. 58) with lattice parameters a = 9.8833(7) Å; b = 7.1251(3) Å; c = 5.0895(4) Å. All sites are fully occupied within the standard deviations. The structure can be described as typical Laves phase, where Cu and As are forming vertex-linked tetrahedra and Cd adopts the structure motive of a distorted diamond network. Cd4Cu7As was prepared from stoichiometric mixtures of the elements in a solid state reaction at 1000 °C. Magnetic measurements are showing a Pauli paramagnetic behavior. During our systematical investigations within the ternary phase triangle Cd–Cu–As the cubic C15-type Laves phase Cd4Cu6.9(1)As1.1(1) was structurally characterized. It crystallizes cubic in the space group Fd3m̅ with lattice parameter a = 7.0779(8) Å. Typically for quasi-binary Laves phases Cu and As are both occupying the 16c site. Chemical bonding, charge transfer and atomic properties of Cd4Cu7As were analyzed by band structure, ELF, and AIM calculations. On the basis of the general formula for Laves phases AB2, Cd is slightly positively charged forming the A substructure, whereas Cu and As represent the negatively charged B substructure in both cases. The crystal structure distortion is thus related to local effects caused by Arsenic that exhibits a larger atomic volume (18 Å3 compared to 13 Å3 for Cu) and higher ionicity in bonding.