The enthalpy of transformation of Ca(OH)2-I (portlandite) to Ca(OH)2-II (EuI2 structure) by low-temperature DSC

 Thermodynamic properties of high-pressure minerals that are not recoverable from synthesis experiments by conventional quenching methods (“unquenchable” phases) usually are calculated from equation of state data and phase diagram topologies. The present study shows that, with cryogenic methods of recovery and sample treatment, phases with a suitable decomposition rate can be made accessible to direct thermodynamic measurements. A set of samples of Ca(OH)₂-II has been synthesized in a multianvil device and subsequently recovered by cooling the high-pressure assembly with liquid nitrogen. Upon heating from liquid nitrogen to room temperature, the material transformed back to Ca(OH)₂-I. The heat effect of this backtransformation was measured by differential scanning calorimetry. A commercial differential scanning calorimeter (Netzsch DSC 404), modified to allow sample loading at liquid nitrogen temperature was used to heat the material from −150 to +200 °C at rates varying between 5 and 15 °C min⁻¹. The transformation started around −50 °C very gradually, and peaked at about 0 °C. To obtain a baseline correction, each sample was scanned under exactly the same conditions after the backtransformation was complete. Because of the relative sluggishness, onset and offset temperatures were not well defined as compared to fast (e.g., melting) reactions. To aid in integration, the resulting signals were successfully fitted using a generic asymmetric peak model. The enthalpy of backtransformation was determined to be ΔH =−10.37 ± 0.50 kJ mol⁻¹. From previous in situ X-ray diffraction experiments, the location of the direct transformation in P-T space has been constrained to 5.7 ± 0.4 GPa at 500 °C (Kunz et al. 1996). With the reaction volume known from the same study, and assuming that ΔC _p of the transformation remains negligible between the conditions of our measurements and 500 °C, our result gives an estimate of the entropy of transition and the P-T slope of the reaction curve. To a first approximation, the values ΔS = −16.00 ± 0.65 J(mol · K)⁻¹ and dP/dT = 0.0040 ± 0.0002 GPa/K have been determined. These results need to be refined by equation of state data for Ca(OH)₂-II. Received: 30 December 1999 / Accepted: 10 April 2000     

In situ neutron diffraction study of deuterated portlandite Ca(OD)2 at high pressure and temperature

The structure of deuterated portlandite, Ca(OD)₂, has been investigated using time-of-flight neutron diffraction at pressures up to ∼4.5 GPa and temperatures up to ∼823 K. Rietveld analysis of the data reveals that with increasing pressure, unit-cell parameter c decreases at a rate about 4.5 times larger than that for a, which is largely due to rapid contraction of the interlayer spacing in this pressure range. Fitting of the determined cell volumes to the third-order Birch–Murnaghan equation of state yields a bulk modulus (K ₀) of 32.2 ± 1.0 GPa and its first derivative (K ₀′) of 4.4 ± 0.6. Moreover, on compression, hydrogen-mediated interatomic interactions within the interlayer become strengthened, as reflected by decreases in interlayer D···O and D···D distances with increasing pressure. Correspondingly, D–D, the distance between the three equivalent sites over which D is disordered, increases, suggesting a pressure-induced hydrogen disorder. This behavior is similar to that reported in brucite at elevated pressure. On heating at ∼2.1 GPa, cell parameter c increases more rapidly than a, as expected. However, because of the pressure effect, the thermal expansion coefficients, particularly along c, are much smaller than those at ambient pressure. With increasing temperature, the three partially occupied D sites become further apart, and the D-mediated interactions, mainly the interlayer D···D repulsion, become weakened.     

P-V equation of state of portlandite, Ca(OH)2, from powder neutron diffraction data

 A high pressure neutron powder diffraction study of portlandite [Ca(OH)₂] has been performed at ISIS facility (U.K.); nine spectra have been collected increasing the pressure by steps, up to 10.9 GPa, by means of a Paris-Edinburgh cell installed on the POLARIS diffractometer. The tensorial formalism of the lagrangian finite strain theory and the Birch-Murnaghan equation of state have been used to determine, independently, two values of the bulk modulus of portlandite, obtaining K ₀=38.3(±1.1) GPa [linear incompressibilities: K _0a=188.4(±9.9), K _0c=64.5(±2.5) GPa] and K ₀=34.2(±1.4) GPa, respectively. The present results comply with values from previous measurements by X-ray diffraction [K ₀=37.8(±1.8) GPa] and Brillouin spectroscopy [K ₀=31.7(±2.5) GPa]. Reasonably, Ca(OH)₂ has revealed to be bulkly softer than Mg(OH)₂ [K ₀=41(±2), K _0a=313, K _0c=57 GPa]. The Ca(OH)₂ linear incompressibility values reflect the nature of forces acting to stabilize the (001) layer structure and, further, prove that the replacement Ca/Mg mainly affects the elastic properties in the (001) plane, rather than along the [001] direction. Data from a full refinement of the structure at room pressure are reported. Received January 12, 1996/Revised, accepted June 15, 1996     

Characterisation of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

Tobelite (NH₄) Al₂ [AlSi₃O₁₀] (OH)₂, the ammonium analogue of muscovite, and its deuterated form ND₄-tobelite (ND₄) Al₂ [AlSi₃O₁₀] (OD)₂ have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO₂-Al₂O₃ oxide mix with Al₂O₃ in excess of 5 mol% and a 25% NH₃ solution whose relative abundance was such that the amount of NH₄ ⁺ stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND₄-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K⁺ in muscovite, the NH₄ ⁺ or ND₄ ⁺ molecule occupies the interlayer site. IR absorption bands caused by NH₄ ⁺ and ND₄ ⁺ can be explained, to a very good approximation, on the basis of T_d symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal T_d symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K⁺ by NH₄ ⁺ has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND₄-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M ₁ (C2/c) and 2M ₂ (C2/c). Tobelite and ND₄-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND₄-tobelite synthesised at 200 Mpa, is 2M ₂. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH₄ ⁺ or ND₄ ⁺ compared to K⁺ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND₄-tobelite.     

Bearthite,Ca2Al(PO4)2OH: stability,thermodynamic properties and phase relations

Contributions to Mineralogy and Petrology - The new phosphate bearthite, Ca2Al(PO4)2HO, found in high-pressure metamorphic rocks, has been synthesized from a stoichiometric mixture of γ-Al2O3...     

Compression and amorphization of (Mg,Fe)2SiO4 olivines: An X-ray diffraction study up to 70 GPa

The effect of (Mg,Fe) substitution on the compression and pressure-induced amorphization of olivines has been investigated up to more than 50 GPa in a diamond anvil cell through energy-dispersive X-ray diffraction experiments with synchrotron radiation. For the four (Mg_1–x , Fe _x )₂SiO₄ olivines studied, the compressibility is the highest along the b axis and the smallest along the a axis. For compositions with x = 0, 0.17, 0.66, and 1, the slope of the volume-pressure curves shows a rapid decrease at pressures of around 42, 34, 20 and 10 GPa, respectively. Assuming K₀ = 4, we obtained at lower pressures with a Birch-Murnaghan equation of state essentially the same room-pressure bulk modulus for all olivines, namely K ₀ = 131 ± 6 GPa, in agreement with previous single-crystal compression and ultrasonic measurements. At higher pressures, the compression becomes nearly isotropic and the materials very stiff. These changes could precede partial transformation of olivines to a high-pressure polymorph related to the spinel structure. Only a small fraction of olivines seems to transform actually to this phase, however, because most of the material undergoes instead pressure-induced amorphization which take place at considerably higher pressures for Mg-than for Fe-rich olivines.     

High pressure elasticity and phase transformation in brucite, Mg(OH)2

The first pressure derivatives of the second-order elastic constants have been calculated for brucite, Mg(OH)₂ from the second- and third-order elastic constants. The deformation theory and finite strain elasticity theory have been used to obtain the second- and third-order elastic constants of Mg(OH)₂ from the strain energy of the lattice. The strain energy ϕ is calculated by taking into account the interactions up to third nearest neighbors in the Mg(OH)₂ lattice. ϕ is then compared with the strain dependent lattice energy from continuum model approximation to obtain the expressions of elastic constants. The complete set of six second-order elastic constants C _IJ of brucite exhibits large anisotropy. Since C ₃₃ (= 21.6 GPa), which corresponds to the strength of the material along the c-axis direction, is less than the longitudinal mode C ₁₁ (= 156.7 GPa), the interlayer binding forces are weaker than the binding forces along the basal plane of Mg(OH)₂. The 14 nonvanishing components of the third-order elastic constants, C _IJK , of brucite have been obtained. All the C _IJK of brucite are negative except the values of C ₁₁₄ (= 230.36 GPa), C ₁₂₄ (= 75.45 GPa) and C ₁₃₄ (= 36.98 GPa). The absolute values of the C _IJK are, in general, one order of magnitude greater than the C _IJ ’s in the Mg(OH)₂ system as usually expected for a crystalline material. To our knowledge, no previous data are available to compare the pressure derivatives of brucite. The pressure derivatives of the two components viz., C ₁₄ and C ₃₃ become negative indicating an elastic instability in brucite while under pressure. This may be related to the phase transition of brucite largely involving rearrangements of H atoms revealed in the Raman spectroscopic, powder neutron diffraction and synchrotron X-ray diffraction studies.     

Solubility of rare earth elements in carbonatite magmas,indicated by the liquidus surface in CaCO3Ca(OH)2La(OH)3 at 1 kbar pressure

The system CaCO₃Ca(OH)₂(CCCH) represents a synthetic analog to a carbonatite magma. Addition of a light rare earth (RE) component La(OH)₃ (LH) gives a simple analog of a rare earth carbonatite. Liquidus relations for two joins were studied at 1 kbar pressure; CHLH and (CC₅₅CH₄₅)LH. CHLH is binary with a eutectic at CH₇₉LH₂₁ and 710°C. Thejoin CC₅₅ + CH₄₅)LH has a liquidus piercing point between CC and LH, at (CC₅₅CH₄₅)₆₀LH₄₀ and 700°C. Combining the new results with known results for CCCH allows construction of a liquidus diagram for part of the join CCCHLH. A ternary eutectic between the primary liquidus fields for CH, CC and LH occurs near 610°C with estimated composition CC= 33%,CH= 47%,LH= 20%. The solubility of La(OH)₃ in the synthetic carbonatite magma increases with increase of CO₂/H₂O from 20% at the eutectic to 40% at the piercing point on the join (CC₅₅CH₄₅)LH. The solubility of La in synthetic carbonatite is high compared with that of silicates. P₂O₅, and S. The results show that REE can become concentrated to high levels by fractionation of carbonatites, as long as they are not removed by high temperature crystallization of apatite and monazite.     

Synthesis and Stability Relations of Epidote, Ca2Al2FeSi3O12 (OH)

Hydrothermal investigation of the bulk composition 2CaO·Al₂O₃·l/2Fe₂O₂·3SiO₂+excessH₂O (Ps 33 +excess H₂O) has been conducted using conventionalapparatus and solid oxygen buffer techniques. Coarse-grainedepidotes (over 150 microns in some cases) were readily synthesizedfrom oxide mixtures with a 98 per cent yield as well as fromtheir high temperature equivalents at 600–700 °C and5 kb P_fluid and over a range of oxygen fugacities. Electronmicroprobe analyses show that maximum Fe⁺³ content of syntheticepidotes varies as a function of fo₂. Epidote is most iron-rich(Ps 33 ± 2) at high (HM and CCO) oxygen buffers and becomesprogressively more aluminous (Ps 25 ± 3) with decreasingfo₂ values and temperatures. Such variation is consistent withthe change of refractive indices and cell dimensions. The meanrefractive indices and cell dimensions for synthetic epidote(Ps 33) are N = 1.745 ± 0.005, N = l.786±0.005,a = 8.920±0.005 Å, b = 5.645±0.004 Å,c = 10.190 ű0.006 Å, and ß = 115°31'±4' and for epidote (Ps 25) are N = 1.735±0.005,N = 1.775±0.005, a = 8.891±0.005 Å, b =5.625±0.004 Å, c = 10.177±0.006 Å,and ß = 115° 30'±3'. Mössbauer spectraindicate synthetic epidotes are relatively disordered. Garnets of intermediate composition in the grossular-andraditeseries were synthesized and the cell dimensions and refractiveindices vary linearly with composition. With successive decreasein fo₂, garnet synthesized on the Ps 33 bulk composition movestoward the grossular end member with simultaneously increasingalmandine component; concomitantly the hercynite component ofthe coexistent magnetite increases. The fo₂-T-P_fluid relations were determined by employing mineralmixtures of synthetic epidote and its high temperature equivalentin subequal proportions. Equilibrium was demonstrated for thereactions (1) epidote (Ps 33) = anorthite+grandite+FeO_x+quartz+ fluid, and (2) epidote (Ps 25) (+quartz) = garnet₃₈+anorthite+magnetitc+fluid.With fo₂ defined by the HM buffer, epidote (Ps 33) is stableup to 748 °C, 5 kb, 678 °C, 3 kb, and 635 °C, 2kb P_fluid. With fo₂ defined by the NNO buffer, the epidote (Ps25) high temperature stability limit is reduced about 100 °Cat 5kb P_fluid. At slightly lower fo₂, than defined by the QFMbuffer, epidote is not stable at any temperatures; the assemblagehedenbergite+anorthite+garnet₃₈+fluid replaces epidote in thepresence of excess quartz. Combined with previously determined equilibria for prehnite,andradite, and hedenbergite, isobaric fo,-T relations were furtherinvestigated by chemographic analysis interrelating the phasesprehnite, epidote, grandite, hedenbergite, wollastonite, anorthite,and magnetite in the system CaO-Fe₂O₃-Al₂O₃-SiO₂-H₂0. Such analysisallowed the construction of a semi-quantitative petrogeneticgrid applicable to natural parageneses in low µCO₂ environments,and the delineation of the low temperature stability limit ofepidote as a function of fo₂. Enlargement of the epidote stabilityrange toward both high and low temperatures with increasingfo₂, is consistent with widespread occurrences of epidote inlow- and mediumgrade metamorphic rocks.     

Solubility of niobium in the system CaCO3–Ca(OH)2–NaNbO3 at 0.1 GPa pressure

Experimental data are presented for the solubility of NaNbO₃ in the ternary system CaCO₃-Ca(OH)₂-NaNbO₃ (or calcite-portlandite-lueshite) over the temperature range 500-950 °C at 0.1 GPa pressure. Near-liquidus phase relationships are given for the pseudo-binary join ([CaCO₃]₄₅[Ca(OH)₂]₅₅)_100-x-(NaNbO₃)_x; (0 <x <70 wt%). These data show the presence of a large field of calcite plus liquid and the absence of NaNbO₃ as a primary liquidus phase until the melts contain greater than 60 wt% NaNbO₃. The primary crystallization fields of calcite and NaNbO₃ are separated by a steep thermal valley located at about 55 wt% NaNbO₃. Quenched liquids contain calcite, portlandite, sodium carbonates and perovskite-structured calcium niobates. The maximum solubility of Nb₂O₅ in this system is estimated to be on the order of 48 wt% at 650 °C at 0.1 GPa pressure. The experiments show that perovskite-structured compounds rather than pyrochlore crystallize from these fluorine-free, water-rich melts.     

高铬刚玉：湖南沅水金刚石包裹体中发现的一种高压矿物

对湖南沅水金刚石中的包裹体矿物含铬刚玉进行了矿物学研究。确认合铬刚玉中铬的最高质量分数可达19．31％。根据EPMA分析,高铬刚玉的晶体化学分子式为（All683,Cro298,Fe0.010,Mn0．008,T10．0。4,Sb．001）2．0040s,获得了该样品的X射线粉末衍射图谱,并在此基础上进行了Rietve...     

Thermal expansion of Mg(OH)<Subscript>2</Subscript> brucite under high pressure and pressure dependence of entropy

An equation of state for Mg(OH)₂ brucite under high-pressure and high-temperature conditions has been obtained by measuring temperature dependence of volume up to 600 K at ambient pressure and pressure dependence of volume up to 16 GPa at 300, 473, 673, and 873 K with in situ X-ray diffraction. Pressure dependence of entropy of brucite has been calculated with thermal expansion coefficient and volume which are derived from the present EoS. This dependence indicates that generation of secondary OH dipoles affects entropy. The OH dipoles probably appear around 2 GPa and the number seems not to change over 8 GPa at 300 K.     

致密砂岩高围压和高孔隙水压下渗透率演化规律及微观机制

深部岩石工程具有高地应力和高水头压力的特点。为了研究岩石在高围压和高孔隙水压条件下渗透率演化规律,选取致密砂岩开展不同围压条件下变孔隙水压的渗流试验。研究结果表明:(1)在所研究的围压范围内(0~50 MPa),随孔隙压力增加,渗透率依次呈现3种不同的变化趋势,即快速增长阶段(围压为10~20 MPa)、缓慢增长阶段(围压为30~40 MPa)和保持恒定阶段(围压为50 MPa);在围压卸载时,由于高围压作用使试样内部产生不可逆变形,导致渗透率具有明显的不可恢复现象,且随围压降低,渗透率恢复存在滞后效应。(2)渗流试验过程中,体积应变和渗透率演化具有较好的一致性。(3)在围压加卸载过程中,高孔隙水压力条件下渗透率对应力的敏感程度和恢复程度均大于低孔隙水压力。(4)偏光显微镜图像从微观角度揭示了试样在围压加卸载过程中产生不可逆变形的内在机制:骨架颗粒相互挤压、错动导致原有微裂隙压缩、孔隙减小甚至坍塌,引起渗透率不可恢复。渗流试验后,纵波波速增大,说明岩石致密性提高,与试样内部微观结构变化具有较好的一致性。     

Hydrogen bonding in basic copper salts: a spectroscopic study of malachite,Cu2(OH)2CO3, and brochantite,Cu4(OH)6SO4

Infrared and Raman spectra of the basic copper salts malachite, Cu₂(OH)₂CO₃, and brochantite, Cu₄(OH)₆SO₄, as well as of deuterated and ¹³C substituted samples are presented and discussed in terms of group theory and the hydrogen bonds present. The main results are that (i) the hydrogen donor strengths of the OH^? ions are strongly increased due to the very great synergetic effect of the copper ions, (ii) the acceptor strengths of the H-bond acceptor groups (SO₄ ^2-, CO₃ ^2-, and OH^? ions) are significantly modified by the linkage and coordination of the acceptor atoms — this complicates true assignment of the OH bands observed to the two and six different OH^? ions present in malachite and brochantite, respectively -, and (iii) the Cu — O stretching modes at 430–590 cm^?1 and 420–520 cm^?1 for malachite and brochantite, respectively, exhibit strong, partially covalent Cu — O bonding.     

Mechanical twinning in diopside Ca(Mg,Fe)Si2O6: Structural mechanism and associated crystal defects

Diopside twins mechanically on two planes, (100) and (001), and the associated macroscopic twinning strains are identical (Raleigh and Talbot, 1967). An analysis based on crystal structural arguments predicts that both twin mechanisms involve shearing of the (100) octahedral layers (containing Ca²⁺, Mg²⁺ and Fe²⁺ ions) by a magnitude of c/2. Small adjustments or shuffles occur in the adjacent layers containing the [SiO₄]^4? tetrahedral chains. While the (100) twins are conventional with shear parallel to the composition plane, this analysis predicts that (001) twins form by a mechanism closely related to kinking. A polycrystalline diopside specimen was compressed 8% at a temperature of 400° C, a pressure of 16 kilobars, and a compressive strain rate of about 10^?4/s. Transmission electron microscopy on this specimen has revealed four basic lamellar features:

1. (100) mechanical twin lamellae;
2. (100) glide bands containing unit dislocations;
3. (001) twin lamellae;
4. (101) lamellar features, not as yet identified.

The (001) twins often contain remnant (100) lamellae of untwinned host. Twinning dislocations occur in these (100) lamellae and in the (001) twin boundaries with very high densities. Diffraction contrast experiments indicate that the twinning dislocations associated with both twin laws glide on (100) with Burgers vector b=X [001] where X is probably equal to 1/2 on the basis of the structural analysis. Parallels are drawn between mechanical twinning in clinopyroxenes and clinoamphiboles. The exclusive natural occurrence of basal twins in shock-loaded clinopyroxenes and of analogous ( \(\bar 1\) 01) twins in clinoamphiboles is given a simple explanation in terms of the relative difficulty of the “kinking” mechanism as compared to direct glide parallel to the composition plane.     

Crystal chemistry of titanite-structured compounds: the CaTi1-x Zr x OSiO4 (x≤0.5) series

Inhomogeneous aggregates of late-stage titanite enriched in Zr have been described recently from post-magmatic parageneses in silica-undersaturated rocks. In the natural samples, simple isovalent substitution of the large Zr (^[vi]R⁴⁺=0.72 Å) for Ti (^[vi]R⁴⁺=0.605 Å) is limited to an empirical maximum of 0.25 afu (15.3 wt.% ZrO₂). As the natural material is not suitable for crystallographic study, a series of CaTi_1-xZr_xOSiO₄ titanite samples have been synthesized by standard ceramic methods at ambient pressure in air, and their crystal structure determined by Rietveld refinement of laboratory powder X-ray diffraction patterns. All of the synthetic Zr-doped titanite varieties adopt space group A2/a and consist of distorted CaO₇ polyhedra together with less distorted (Ti_1-xZr_x)O₆ octahedra and SiO₄ tetrahedra. Cell dimensions and atomic coordinates together with volumes and distortion indices are given for all polyhedra. The empirical limit for Zr substitution in synthetic (F,OH)-free titanite is 0.5 afu (29.6 wt.% ZrO₂). The existence of a Zr analogue of titanite in nature is considered to be unlikely.     

利用尾矿砂制备镁铁氢氧化物实验研究

以金川铜镍矿尾矿酸浸液为原料,根据矿物沉淀pH值区间的不同,分步分离Fe、Mg的沉淀物以及有价金属Al、Co、Ni、Cu的混合沉淀物,进而制备具有高附加值的Fe(OH)3和Mg(OH)2,同时富集Co、Ni、Cu等有价金属。结果表明,当溶液pH值为3.8时可沉淀分离出主要成分为施威特曼石(schwertmannite)的氢氧化铁前驱体,pH值达到9.8时沉淀富集出Al、Co、Ni、Cu的混合氢氧化物,随即得到只含有Mg离子的溶液。在60℃条件下,将施威特曼石在pH值为12的NaOH溶液中老化36h,可以得到Fe(OH)3。同时,以NaOH调节只含有Mg离子的溶液至pH值为12.4时可获得Mg(OH)2。本研究为金属矿山尾矿的资源化综合利用提供了新的思路与方法。     

Crystal structure and chemical formula of schmiederite,Pb2Cu2(OH)4(SeO3)(SeO4), with a comparison to linarite,PbCu(OH)2(SO4)

Summary Based on a X-ray structure analysis it was proved that the mineral schmiederite contains both selenite and selenate groups [a = 9.922(3)Å,b = 5.712(2)Å,c = 9.396(3)Å, = 101.96(3)°, space group P2₁/m,Z = 2 {Pb₂Cu₂(OH)₄(SeO₃)(SeO₄)},R _w = 0.055 for 1131 reflections up to sin / = 0.65 Å^–1]. The crystal structure is closely related to that of linarite [a = 9.701(2) Å,b = 5.650(2) Å,c= 4.690(2)Å, = 102.65(2)°, space group P2₁/m,Z = 2 {PbCu(OH)₂(SO₄)},R _w = 0.034 for 1991 reflections up to sin / = 1.0 Å^–1].The Pb atom in linarite and the Pb(1) atom in schmiederite have each three Pb-O bonds < 2.45 Å with trigonal pyramidal arranged ligands; the Pb(2) atom in schmiederite has only one such near O atom. The Cu atoms are approximately square planar coordinated by hydroxil groups. In addition two further O atoms complete the coordination figure to a strongly distorted octahedron. All the anion groups have the usual geometry.

---

Kristallstruktur und chemische Formel von Schmiederit, Pb₂Cu₂(OH)₄(SeO₃)(SeO₄), mit einem Vergleich zu Linarit, PbCu(OH)₂(SO₄)

Zusammenfassung Basierend auf einer Röntgen-Strukturuntersuchung konnte das Vorliegen von Selenit-und Selenatgruppen im Mineral Schmiederit belegt werden [a=9,922(3) Å,b = 5,712(2) Å,c = 9,396(3) Å, = 101,96(3)°, Raumgruppe P2₁/m,Z=2 {Pb₂Cu₂(OH)₄(SeO₃)(SeO₄)},R _w = 0,055 für 1131 Reflexe bis sin /, = 0,65 Å^–1]. Die Kristallstruktur weist enge Beziehungen zu jener des Linarits auf [a = 9,701(2) Å,b = 5,650(2) Å,c = 4,690(2) Å, = 102,65(2)°, Raumgruppe P2₁/m,Z=2 {PbCu(OH)₂(SO₄)},R _w = 0,034 für 1991 Reflexe bis sin / = 1,0 Å^–1].Das Pb-Atom im Linarit sowie das Pb(1)-Atom im Schmiederit haben jeweils drei Pb-O-Bindungen <,45 Å, wobei die Liganden trigonal pyramidal angeordnet sind; das Pb(2)-Atom im Schmiederit hat hingegen nur ein derart nahes O-Atom. Die Cu-Atome sind etwa quatratisch planar von Hydroxilgruppen koordiniert; zwei weitere O-Atome ergänzen die Koordinationsfigur zur einem stark verzerrten Oktaeder. Die Aniongruppen haben die üblichen Dimensionen.