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1.
Summary A suite of 19 rutiles form a wide range of geological environments shows a distinct variability in the OH concentrations. The analytical H2O+ content determined by IR spectroscopy varies from 0.04 to 0.21 wt.% with the greatest amounts occurring in amphibolite facies rutiles. The main feature of the IR spectra in the region of the OH stretching fundamental is a single narrow band centered at 3280 cm–1; some of the spectra show an additional band, centered either at 3360 or at 3320 cm–1. Varying OH concentrations in rutiles are probably a function of the activity of hydrous components during crystallization and are weakly correlated to a minor content of tri- and pentavalent elements.
Die Variation in der OH Konzentration von Rutilen unterschiedlicher geologischer Vorkommen
Zusammenfassung Eine Serie von 19 Rutilen aus unterschiedlichen geologischen Vorkommen zeigt eine deutliche Variabilität in den OH Konzentrationen. Der IR spektroskopisch bestimmte analytische H2O+-Gehalt variiert von 0.04 bis 0.21 Gew.%, wobei die höchsten Gehalte in Rutilen der Amphibolitfacies auftreten. Das wesentliche Merkmal der IR Spektren im Bereich der OH Streckschwingung ist eine einzelne schmale Bande bei 3280 cm–1; einige der Spektren zeigen entweder bei 3360 oder bei 3320 cm–1 eine zusätzliche Bande. Wahrscheinlich stellen die variierenden OH Konzentrationen, die mit einem geringen Gehalt an drei- und fünfwertigen Elementen schwach korreliert sind, eine Funktion der Wasser-Aktivitäten bei der Kristallisation dar.
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2.
Summary Vivianite from Catavi Mine, Llallagua, Bolivia, has a near ideal composition with traces of Mg, Zn and Mn. Total rare-earth elements are < 1,gmg/g. Mössbauer spectroscopy shows FeIII/(FeII + FeIII) is approximately 0.04.a = 10.030Å,b = 13.434Å,c = 4.714Å, = 102.73dg. The middle-infrared powder spectrum shows H2O-related bands at 3490, 3290, 3130 cm–1 (stretch), 1618 cm–1 (bend), 825 cm–1 (rock), and at 665 cm–1 a possible M-OH2 twist. P04 bands occur at 1045-940 cm–1 (stretch) and 570-450 cm–1 (bend). Corresponding laser Raman microprobe bands occur at 1051 (ms), 986 (m), 948 (vs), 867 (mw), 828 (w), 568, 532, 453 (m), 442 (mw). Weak Raman bands at about 342, 303, 270 (w), 235 (ms), 227 (sh, ms), 196 (ms), 187 (sh, m), 162 (mw), and 126 (m) may arise from lattice vibrations. Differential thermal responses include a major endotherm from 115–235°C with a shoulder at 170°C and a maximum at 210°C resulting from loss of structural water combined with oxidation of Fe2+, and two small exotherms with maxima at 605 and 780°C related to structural transformations.
Charakterisierung des Vivianits von Catavi, Llallagua, Bolivien
Zusammenfassung Vivianit von der Catavi Mine, Llallagua, Bolivien zeigt annähernd ideale Zusammensetzung mit Spuren von Mg, Zn und Mn. Der gesamte Gehalt an seltenen EvolElementen ist < 1 ppm. Die Mössbauer Spektroskopie liefert ein Fe3+/(Fe2+ + Fe3+) Verhältnis von ungefähr 0.04.a = 10.030,b = 13.434,c = 4.714 Å, = 102.73°. Das Infrarot-Pulverspektrum zeigt dem H20 zuzuordnende Banden bei 3490, 3290, 3130 cm–1 (Streckschwingungen), 1618 cm–1 (Deformationsschwingung), 825 cm–1 (Schaukelschwingung) und eine mögliche M-OH2 Torsionsschwingung bei 665 cm–1. PO4 Banden liegen bei 1045-940 cm–1 (Streckschwingung) und 570-450 cm–1 (Deformations-schwingung). Entsprechende Banden der Laser Raman Mikrosonde liegen bei 1051 (mst), 986 (m), 948 (sst) 867 (mschw), 828 (schw), 568, 532, 453 (m), 442 (mschw). Raman Banden bei etwa 342, 303, 270 (schw), 235 (mst), 227 (Schulter, mst), 196 (mst), 187 (Schulter, m), 162 (mschw) und 126 (m) können auf Gitterschwingungen zurückgeführt werden. Differential-thermoanalytische Untersuchungen zeigen einen endothermen Bereich von 115–235°C mit einer Schulter bei 170 und einem Maximum bei 210°C, was auf den Verlust von strukturellem Wasser, das an eine Oxidation des Fe2+ gebunden ist, zurückzuführen ist; zwei auf strukturelle Transformationen zurückzuführende exotherme Maxima liegen bei 605 und 780°C.

With 4 Figures  相似文献   

3.
Summary IR spectra of phenakite single crystals from different localities show a distinct variability in the region of the OH stretching fundamental. Minute hydrous mineral phases (tourmaline, bertrandite) are included in Piracicaba phenakite. Structural OH, ranging up to 0.005 equivalent wt.% H2O, is characterized by two extremely pleochroic bands centered at 3380 and 3120 cm–1. On the basis of their pleochroic scheme it is proposed that (O2(OH)2) and (O3(OH)) tetrahedra occur as structural elements, assuming that the vacancies are on Be sites.
Das Auftreten von OH Absorptionen in Phenakit—eine IR spektroskopische Untersuchung
Zusammenfassung Die IR Spektren von Phenakit-Einkristallen verschiedener Vorkommen zeigen im Bereich der OH-Streckschwingungen eine deutliche Variabilität. Piracicaba Phenakit enthält feinste Einschlüsse von OH-hältigen Mineralphasen (Turmalin, Bertrandit). Strukturell gebundene OH-Gruppen (bis 0,005 äquivalente Gew.% H2O) sind durch zwei extrem pleochroitische Banden bei 3380 und 3120 cm–1 charakterisiert. Unter der Annahme von Be-Leerstellen werden aufgrund des Pleochroismus dieser Banden (O2(OH)2) und (O3(OH)) Tetraeder als strukturelle Baueinheiten vorgeschlagen.

With 3 Figures  相似文献   

4.
Summary The pleochroic behaviour of a gem-quality enstatite from Tanzania was investigated in the region =2500 to 4000 cm–1. Two sharp absorption bands at =3410 cm–1 and =3510 cm–1 are interpreted to be caused by OH stretching vibrations. As their absorption coefficients are considerably larger parallel to [001] (=direction of the silicate chains) than perpendicular to this direction, the OH dipoles have to be oriented approximately parallel to [001]. On this basis, a stereochemical interpretation of the incorporation of the OH groups into the structure is given.
Der Pleochroismus eines Enstatits von Edelsteinqualität im Gebiet der OH-Streckfrequenz und seine kristallchemische Interpretation
Zusammenfassung Das pleochroitische Verhalten eines Enstatits von Edelsteinqualität aus Tansania wurde im Bereich =2500 bis 4000 cm–1 untersucht. Von zwei scharfen Banden bei =3410 cm–1 und 3510 cm–1 wird angenommen, daß sie durch OH-Streckschwingungen herrühren. Da ihre Absorptionskoeffizienten parallel zu [001] (=Richtung der Silikatketten) beträchtlich größer sind als senkrecht dazu, müssen die OH-Dipole ungefähr parallel zu [001] liegen. Auf dieser Basis wird der Einbau der OH-Gruppen in die Struktur diskutiert.

With 3 Figures  相似文献   

5.
OH structure of metamorphic fluids has been studied by high temperature infrared (IR) microspectroscopy on natural fluid inclusions contained in quartz veins, over the temperature range 25–370 °C. Blueschist-facies veins from Tinos island core complex (Cyclades, Greece) display H2O–NaCl–CaCl2–CO2 inclusions whereas greenschist-facies veins contain H2O–NaCl ± CO2 inclusions. From 25 to 370 °C, peak positions of OH stretching IR absorption bands increase quasi-linearly with slopes of 0.25 and 0.50 cm–1 °C–1 for inclusions trapped under blueschist and greenschist conditions, respectively. Extrapolation to 400 °C yield peak positions of 3,475 cm–1 for blueschist inclusions and 3,585 cm–1 for greenschist inclusions. Because the smaller wave number indicates the shorter hydrogen-bond distance between water molecules, fluids involved in the greenschist event have a loose structure compared with blueschist fluids. We suggest that these properties might correspond to a low wetting angle of fluids. This would explain the high mobility of aqueous fluids suggested by structural observation and stable isotope analysis.Editorial responsibility: J. Hoefs  相似文献   

6.
Summary Kyanites from different occurrences show in the near IR two relatively strong absorption bands at 3 380 and 3 270 cm–1 due to OH stretching frequencies. The integral molar extinction coefficient is 3201 · Mol–1 · cm–2. A quantitative IR spectroscopic microtechnique based on Beer's law allows to determine small amounts of structural OH groups in (100) cleavage plates of a few tenths mm in size proved to be free of inclusions and hydrous alteration products. There exists an obvious relation between the occurrence of the kyanites studied and their equivalent H2O+ content ranging from < 0.005 to 0.180 wt.%.
Die quantitative IR-spektroskopische Bestimmung von strukturell gebundenen OH Gruppen in Kyaniten
Zusammenfassung Kyanite verschiedener Vorkommen zeigen im nahen IR bei 3 380 und 3 270 cm–1 zwei relativ starke Absorptionsbanden, die von OH-Streckfrequenzen herrühren. Der integrale molare Extinktionskoeffizient beträgt 320 1 · Mol–1 · cm–2. Eine auf dem Beerschen Gesetz beruhende quantitative IR-spektroskopische Mikromethode erlaubt kleine Mengen strukturell gebundener OH-Gruppen in (100) Spaltplättchen einiger Zehntelmillimeter Größe, die einschlußfrei und frei von Umwandlungsprodukten sind, zu bestimmen. Es besteht offensichtlich eine Beziehung zwischen dem Vorkommen der untersuchten Kyanite und ihrem äquivalenten H2O+-Gehalt, der sich von < 0.005 bis 0.180 Gew.-% erstreckt.
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7.
Zusammenfassung Die Kristallstruktur des Johannits wurde anhand eines verzwillingten Kristalls von Joachimsthal, Böhmen, mit dreidimensionalen Röntgendaten bestimmt und für 2005 unabhängige Reflexe aufR=0,039 verfeinert. Johannit kristallisiert triklin, RaumgruppeP1, mita=8,903 (2),b=9,499 (2),c=6,812 (2) Å, =109,87 (1) =112,01 (1), =100,40 (1)° undV=469,9 Å3. Chemische Formel und Zellinhalt lauten Cu(UO2)2(OH)2(SO4)2·8H2O, das ist um zwei H2O-Moleküle mehr als bisher angenommen. In der Struktur sind pentagonal dipyramidale (UO2)(OH)2O3-Polyeder paarweise über eine von zwei OH-Gruppen gebildete Kante zu Doppelpolyedern und diese wiederum durch SO4-Gruppen zu (UO2)2(OH)2(SO4)2-Schichten parallel (100) verknüpft. Die Schichten sind parallel über gestreckte Cu(H2O)4O2-Oktaeder und Wassermoleküle miteinander verbunden. Folgende Bindungslängen wurden gefunden: U–O=1,78 Å (2x) und 2,34–2,39 Å (5x); Cu–O=1,97 Å (4x) und 2,40 Å (2x); =1,47 Å; O–O in Wasserstoffbrücken 2,71–2,91 Å (8x) und 3,30 Å.
The crystal structure of johannite, Cu(UO2)2(OH)2(SO4)2·8H2O
Summary The crystal structure of johannite has been determined from threedimensional X-ray data measured on a twinned crystal from Joachimsthal, Böhmen, and has been refined toR=0.039 for 2005 independent reflections. Johannite crystallizes triclinic, space groupP1, witha=8.903 (2),b=9.499 (2),c=6.812 (2) Å, =109.87(1), =112.01(1), =100.40 (1)° andV=469.9 Å3. Chemical formula and cell content are Cu(UO2)2(OH)2(SO4)2·8H2O, by two H2O molecules more than previously assumed. Pairs of pentagonal dipyramidal (UO2) (OH)2O3 polyhedra form double polyhedra by edgesharing via two OH groups. The double polyhedra are linked by the SO4 tetrahedra to form layers (UO2)2(OH)2(SO4)2 parallel zu (100). These layers are interconnected parallel toa by elongated Cu(H2O)4O2 octahedra and water molecules. Following bond lengths have been observed: U–O=1.78 Å (2x) and 2.34–2.39 Å (5x); Cu–O=1.97 Å (4x) and 2.40 Å (2x); =1.47 Å; O–O for hydrogen bonds 2.71–2.91 Å (8x) and 3.30 Å.

Mit 2 Abbildungen  相似文献   

8.
Summary The mineral fibroferrite has the chemical formula Fe(OH)SO4·xH2O; the value forx has not been definitely settled, but as a rule it is found to be near five. Several symmetries are given in the literature.A sample from Saint Felix de Paillères, France, proved to be rhombohedral with space group R3; lattice constants for the hexagonal cell area=24.176,c=7.656 Å. As calculated from the experimental density (=1.95 g·cm–3)Z=18 for this cell. Intensities were collected on an automated X-ray diffractometer from a thin fiber extended along [00.1]. The structure was determined by Patterson and Fourier methods. Least squares refinement with 818 observed reflections resulted inR=0.076.The structure contains hydroxo-bridged {Fe(OH)(H2O)2SO4} spiral chains built of [Fe(OH)2(H2O)2O2] octahedra and SO4 tetrahedra. Hydrogen bonds provide connections between these chains. The spiral chains are a stereoisomer variant of the hydroxo-bridged linear chains of Fe(OH)SO4, butlerite and parabutlerite. A comparison of these compounds is givenm to understand the relationship between the structure and their water content.
Fibroferrit: Ein Mineral mit einer {Fe(OH)(H2O)2SO4} Spiralkette und seine Beziehung zu Fe(OH)SO4, Butlerit und Parabutlerit
Zusammenfassung Das Mineral Fibroferrit hat die chemische Formel Fe(OH)SO4·xH2O; der Wert furx scheint nicht endgültig geklärt zu sein, liegt aber meist nahe 5. Verschiedene Symmetrien werden in der Literatur angegeben.Eine Probe von Saint Felix de Paillères, Frankreich, erwies sich als rhomboedrisch mit der Raumgruppe R3; die Gitterkonstanten der hexagonalen Zelle sinda=24,176,c=7,656 Å. Die experimentelle Bestimmung der Dichte (=1,95 g·cm–3) führt für diese Zelle zuZ=18. Von einer nach [00.1] gestreckten dünnen Faser wurden die Intensitäten auf einem automatischen Röntgendiffraktometer gesammelt. Die Struktur wurde mit Patterson-und Fouriersynthesen gelöst. Eine Verfeinerung nach der Methode der kleinsten Quadrate führte für 818 beobachtete Reflexe aufR=0,076.Die Struktur enthält durch Hydroxil-Gruppen verknüpfte {Fe(OH)(H2O)2SO4}-Spiralketten, die aus [Fe(OH)2(H2O)2O2]-Oktaedern und SO4-Tetraedern aufgebaut sind. Die Spiralketten von Fibroferrit sind eine stereoisomere Variante der annähernd linearen Fe–O–S-Ketten von Fe(OH)SO4, Butlerit und Parabutlerit. Diese Verbindungen werden mit Fibroferrit verglichen, um Beziehungen zwischen Struktur und Wassergehalt zu verstehen.

With 2 Figures

Paper presented at the Fifth European Crystallography Meeting, Copenhagen, Denmark 1979.  相似文献   

9.
Summary The stability field of scorzalite (FeAl2[OH/PO4]2) was investigated in the P-T range from 487 to 684 °C and 0.1 to 0.3 GPa. in hydrothermal experiments. The oxygen fugacity was fixed by the Ni/NiO buffer. Scorzalite shows a decomposition according to the reaction: FeAl2[OH/PO4]2) FeAlPO5 + AlPO4 (berlinite) + H2O. The mean standard enthalpy and standard entropy of reaction were determined as H R 0 = 94(13) kJ, ASR = 180(16) JK–1. A57Fe-Mößbauer spectroscopic examination showed that about 4 atomic % of the total Fe in scorzalite is trivalent.
Experimentelle Bestimmung der thermischen Stabilität von Skorzalith, FeAl2[OH/ PO4]2, und das Auftreten von Lazulith-Skorzalith Mischkristallen unter den Bedingungen der Amphibolithfazies
Zusammenfassung Das Stabilitätsfeld von Skorzalith (FeAl2[OH/PO4]2) wurde im P-T-Bereich zwischen 487 und 684 °C und zwischen 0.1 und 0.3 GPa in Hydrothermalexperimenten unter der Sauerstoffugazität des Ni/NiO-Puffers untersucht. Skorzalith zerfällt unter diesen Bedingungen gemäß der Reaktion: FeAl2[OH/PO4]2) FeAlPO5 + AlPO4 (Berlinit) + H2O. Die Reaktionsenthalpie und -entropie für Standardbedingungen wurden zu H R 0 = 94(13) kJ und ASR = 180(16) JK–1 bestimmt.57 Fe-Mößbaueruntersuchungen ergaben, daß ungefähr 4% des Gesamteisens in Skorzalith dreiwertig vorliegen.

With 4 Figures  相似文献   

10.
Orthorhombic amphiboles with excess OH, which can be schematically deduced from anthophyllite by the combined substitutions Mg2+ + O2–Li++OH– and Mg2+2 Li+, were synthesized at 750–875° C/1 kbar in the system Li2O-MgO-SiO2-H2O. Their phase relations are presented for 800° C/1 kbar . An amphibole with the analytical composition 2.70 wt% Li2O, 31.1 wt% MgO, 63.0 wt% SiO2, and 3.29 wt% H2O has lattice constants a 0 18.588 (11), b 0 17.966 (10), c 0 5.262 (3) Å, V 0 1,757.2 (1.5) Å3 (referred to Space Group Pnma). The OH-valence vibrational spectrum of this amphibole showed v OH bands at 3,667, 3,708, and 3,725 (shoulder) cm–1, which are ascribed to OH in the configurations (MgMgMg)-OH, (MgMgMg)-OH-Li (Li in the A-site) of the pseudotrigonal (M1M1M3)-OH arrangement in the amphibole structure, and to Si-OH, respectively. No explanation can at present be offered for an additional shoulder at 3,695 cm–1. The proposed structural formula is (Li0.27 0.73)(Li1.11 Mg0.89)· (Mg5)(Si8.01O21.20(OH)0.80)(OH)2.00.  相似文献   

11.
Summary The crystal structure of curite, of which until now only the arrangement of the U and Pb atoms was known, has been redetermined with a synthetic crystal using three-dimensional X-ray techniques.R=0.043 for 1270 observed reflections. Curite is orthorhombic, space groupPnam-D 2h 16 ,a=12.513,b=13.002,c=8.373 ,Z=6.56 PbO·16UO3·9.44H2O. The structure consists of a novel type of washboard like puckered layers 2 [(UO2)8O8 (OH)6]6– formed by tetragonal bipyramidal [(UO2)O3(OH)] and pentagonal bipyramidal [(UO2)O3 (OH)2] polyhedra. The layers are parallel to {100} and are directly connected by hydrogen bonds. Lead atoms and oxygen atoms (H2O+OH) are located in folds between the layers, helping to connect them. The interlayer atomic positions are slightly disordered and one of them is partially occupied. The variable concentrations of the interlayer atoms are responsible for the changes in chemical composition.The structural formula [Pb8–x (OH)4–2x (H2O)2x ] [(UO2)8(OH)6]2 is suggested for curite;x=1.44 for the investigated synthetic curite. Within the three different U–O polyhedra the axial U–O distances are 1.81–1.88 , the equatorial 2.14–2.57 . The two different Pb atoms have ionic coordinations, each by ten oxygens with Pb–O distances of 2.46–3.32 , on the average 2.82 .
Die Kristallstruktur von Curit, [Pb 6,56 (H 2 O, OH) 4 ] [(UO 2)8 O 8(OH)6]2
Zusammenfassung Die Kristallstruktur von Curit, von der bisher nur die Lagen der Uran- und Bleiatome bekannt waren, wurde anhand eines künstlichen Kristalls mit dreidimensionalen Röntgendaten neu bearbeitet und für 1270 Reflexe aufR=0,043 verfeinert. Curit kristallisiert rhombisch, RaumgruppePnam-D 2h 16 ,a=12,513,b=13,002,c=8,373 ,Z=6,56 PbO·16 UO3·9,44 H2O. Die Struktur enthält gewellte Schichten eines neuen Typs, 2 [(UO2)8O8(OH)6]6–, die sich aus tetragonal bipyramidalen [(UO2)O3(OH)]- und pentagonal-bipyramidalen [(UO2)O3(OH)2]-Polyedern zusammensetzen. Die Schichten verlaufen parallel {100} und sind über Wasserstoffbrücken miteinander unmittelbar verknüpft. Zwischen den Schichten befinden sich Bleiatome und zusätzliche Sauerstoffatome (H2O+OH). Diese Atome weisen zum Teil Fehlordnung auf; eine der beiden Pb-Lagen ist nur partiell besetzt. Für Schwankungen in der chemischen Zusammensetzung von Curit ist der unterschiedliche Gehalt an Zwischenschichtatomen verantwortlich. Aufgrund dieser Untersuchung wird die Strukturformel [Pb8–x (OH)4–2x (H2O)2x ] [(UO2)8O8(OH)6]2 vorgeschlagen; für den untersuchten Curit istx=1,44. Die drei verschiedenen U–O-Polyeder der Struktur besitzen axiale bzw. äquatoriale U–O-Abstände von 1,81–1,88 bzw. 2,14–2,57 . Die zwei Arten von Bleiatomen besitzen eine ionische Koordination; beide sind von 10 Sauerstoffatomen in Abständen von 2,46–3,32 (Mittelwert 2,82 ) umgeben.

With 3 Figures  相似文献   

12.
The join CaMgSi2O6–KAlSi3O8 has been studied at 6 GPa (890–1,500°C) and 3.5 GPa (1,000–1,100°C). K-rich melts in the join produce assemblages Cpx + Grt, Cpx + Opx, Cpx + San, and Cpx + Grt + San at 1,100–1,300°C. At NSansystem<~70 mol%, sanidine is unstable on the solidus and appears at the liquidus, if NSansystem>90 mol%. This explains a scarcity of San in mantle Cpx-rich assemblages and its association with high-K aluminosilicate melt inclusions in diamonds. In absence of San, KCpx is the only host for potassium. The K-jadeite content in KCpx systematically increases with decreasing temperature and reaches 10–12 mol% near the solidus. However, KCpx coexists with San at NSansystem>70 mol% and <1,300°C, being formed via reaction San + L=KCpx. The KJd content in KCpx is controlled by the equilibrium San=KJd + SiO2L that displaces to the right with increasing pressure and decreasing both the temperature and This equilibrium is considered to be responsible for the formation of San lamellae in natural UHP Cpx. In our experiments at 3.5 GPa, garnet is absent whereas the KJd and Ca-Eskola contents in Cpx are low, and the join CaMgSi2O6–KAlSi3O8 is close to binary (with the eutectic Cpx + San + L). Different topologies of the join at 6 and 3.5 GPa define a sequence of mineral crystallization from K-rich aluminosilicate melts during cooling and decompression: from KCpx + Grt without San at P>4 GPa to Cpx + San at P<4 GPa. Similar sequence of assemblages is observed in some eclogitic xenoliths from kimberlites and Grt–Cpx rocks of the Kokchetav Complex (Northern Kazakhstan).  相似文献   

13.
The structural behavior of -eucryptite (LiAlSiO4) has been investigated using infrared (IR) spectroscopy over a temperature range of 20 to 900 K and FT-Raman spectroscopy at room temperature. IR reflectance measurements show that -eucryptite possesses high reflectivity in the far-IR region, as is consistent with its reported superionic conductivity along the c-axis. On heating, the Li-related IR bands near 246 and 300 cm–1 (with A2 symmetry) broadened and weakened dramatically, presumably as a result of Li+ positional disordering along the structural channels parallel to c. The disordering process appears to induce a framework distortion, as is evidenced by the broadening of some vibrations of Si(Al)–O with increasing temperature. A change in slope in the temperature dependence of the phonon frequency near 300 cm–1 and the linewidth of the 760 cm–1 band at 715 K indicates that Li becomes completely disordered above this temperature. In addition, the temperature dependence of the linewidth for the 760 cm–1 band exhibits an additional change in slope at 780 K, implying the existence of an intermediate state within this temperature range. The detailed structure of this intermediate phase, however, needs further study. Our IR data provide no indication of structural changes between room temperature and 20 K.  相似文献   

14.
The mineral ussingite, Na2AlSi3O8(OH), an interrupted tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm–1, and a possible OH librational bending mode at 1295 cm–1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the 1H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and 1H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5–8% Al–Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and 1H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.  相似文献   

15.
Summary A number of micas of varying compositions and polytypism have been selected from the literature for multiple linear regression analysis. The c dimension in micas is found to depend on the sizes of the interlayer cation, di, and tetrahedral cation, dt, as well as on the hydroxyl content, [OH]. The regression equation obtained: cr = 5.415 + 0.071[OH] + 2.098di + 2.335dt with R2 = 90.5%, shows that the three variables affect the c-axis dimension in the order dt > di [OH]. Addition of 2- and 3-layer polytypes to the regression analysis reduces R2 to 87.2%. Application of the regression analysis to synthetic Al-rich biotites from the literature shows that the amount of [A1IVA1VI]1Y[Fe2+, MgSi]–1y in solid solution is limited and always less than [A1VIO]1z[Fe2+, MgOH]–1z (i.e. 0.35 > y z). The maximum value of the vector y in solution is slightly higher than that reported for natural Al-rich biotites.
Die Beziehung zwischen der Gitterkonstante c und den Austauschkomponenten in Glimmern
Zusammenfassung Eine Anzahl von Glimmern unterschiedlicher Zusammensetzung und Polytypie wurde aus der Literatur für eine multiple lineare Regressionsanalyse ausgewählt. Es stellte sich heraus, dass in Glimmern die Gitterkonstante c von den Grössen des Zwischenschicht-Kations di und des tetraedrischen Kations dt abhängt, ferner vorn Hydroxylgehalt, [OH]. Die erhaltene Regressionsgleichung cr = 5,415 + 0,071 [OH] + 2,098di + 2,335dt mit R2 = 90,5% zeigt, dass die drei Variablen die Grösse der c-Achse in der Reihenfolge dt > di [OH] beeinflussen. Der Einschluss von 2- und 3-Schicht Polytypen in die Regressionsanalysen verkleinert R2 auf 87,2%. Die Anwendung der Regressionsanalysen auf synthetische Al-reiche Biotite aus der Literatur zeigt, der Betrag von [A1IVA1VI]1y[Fe2+, MgSi]–1y beschränkt und immer kleiner als [A1VIO]1z[Fe2+, MgOH]–1z (mit 0,35 < y z) ist. Der Maximalwert des Vektors y in Lösung ist etwas grösser als jener, der für natürliche Al-reiche Biotite angegeben wurde.

With 1 Figure  相似文献   

16.
The electric field arising from K+ or Na+ in the A sites of synthetic hydroxyamphiboles of the richterite-tremolite series raises the stretching frequency of adjacent OH groups by about 60 cm–1. In natural amphiboles, however, the increase in frequency is generally only 20–40 cm–1, due, probably, to the effects of such substitutions as F for OH and Al for Si.  相似文献   

17.
From a total of 335 olivine crystal grains, crystallographically orientated platelets and, where possible, parallelepipeds were prepared, chemically analysed by electron microprobe, examined under the polarisation microscope, and studied by polarised FTIR microscope-absorption-spectrometry in the OH vibrational range, 3,000–3,800 cm–1. The 335 crystal grains were extracted from 174 different specimens of Yakutian upper mantle material, including 97 xenoliths that represent all the rock types occurring in all the kimberlites of the Siberian shield. The other specimens were mega- and macrocrysts or inclusions in diamonds and garnets. Analysis of the polarised OH-spectra allowed distinction between hydroxyl in non-intrinsic separate inclusions, NSI, and in isolated local or condensed extended defects, intrinsic to the olivines, ILD or CED, respectively. As the two latter types cannot be distinguished by vibrational spectroscopy, and as they are presumably interconnected by intracrystalline condensation reactions of the type n [ILD][CED]n, we propose to symbolise them as [ILD/CED]. Of the total of 70 polarised OH-bands that were found in the whole set, 17 are caused by NSI, 53 by [ILD/CED]. Total mean integrated OH-band intensities, (̄int)total with ̄int=(||a+||b+||c)int/3, were determined from the spectra. They yielded the contents of structurally unallocated water, using the recent calibration of the IR-method (Bell et al. 2003). The range is 0<wt. ppm (H2O)total<419. Olivines included in diamonds were found to be free of hydroxyl (detection limit of the single crystal IR-spectrometry, ca. 1 wt. ppm water). The total water contents of the different types of olivines increase in the sequence groundmass crystals < megacrysts < macrocrysts. NSI are: (1) Serpentine plus talc with OH in the range 3,704–3,657 cm–1, either polarised along a of the olivine matrix (Pbnm setting) or unpolarised. Approximately 232 olivines out of the 335 contain such NSI. Serpentine and talc occur mostly together, in rare cases one of them alone and if so, mostly talc. (2) Mg-edenite or Mg-pargasite occur rarely and with OH at 3,709–3,711 cm–1. NIS types (1) and (2) are presumably formed by metasomatic alterations of the host olivines, the orientated ones probably in the mantle, the unorientated ones during later stages. (3) The spectra of 23 olivine crystals, displayed specifically a OH-band, polarised c>a>b, at 3,327–3,328 cm–1, an energy typical of OH in hydrous wadsleyite. We assume this phase to be present as NIS in the respective olivines, possibly as relic phase. (4) Weak bands between 3,175 and 3,260 cm–1 polarised along c, are tentatively assigned to molecular water NSI with relatively strong hydrogen bonds to the matrix. We did not find larger clusters of molecular water, i.e. liquid-like water with its characteristic broad band centred at ca. 3,400 cm–1. We did also not find any humite minerals as an NSI. Of the 53 OH-bands intrinsic to olivine, the 29 most abundant and strong ones were subject to further analysis in terms of OH–-bearing structural defects [ILD/CED]. Nearly all these bands are strongly polarised along a. Two bands at 3,672 and 3,535 cm–1 are assigned to boron-related defects, [ILD/CED]B. Five bands at 3,573, 3,563, 3,541, 3,524 and 3,512 cm–1 are intensity-correlated and are assigned to Si-depleted titan-clinohumite-like defects, [ILD/CED](thl). The other, so far unidentified OH of [ILD/CED] are suggested to originate from OH– in different types of (Mg, Fe)-depleted defects recently predicted and discovered by TEM. These are called [ILD/CED](KWK). Eight mostly strong bands of them occur at energies higher than 3,573 cm–1, [ILD/CED](KWK)-H, 13 strong to medium strong bands occur below 3,500 cm–1, [ILD/CED](KWK)-L. Such intrinsic defects may occur alone, [ILD/CED](thl) and [ILD/CED](KWK)-H, or in different combinations with each other, [ILD/CED](KWK)-H+[ILD/CED](thl), [ILD/CED](KWK)-H+[ILD/CED](KWK)-L and [ILD/CED](KWK)-H+[ILD/CED](thl)+[ILD/CED](KWK)-L. Though there are indications that the occurrences of such types and combinations of the intrinsic OH–-bearing defects in the olivines are related to the types and genetic peculiarities of their host rocks, straightforward and simple correlations do not exist. The reasons for this and also for the great number of varieties of intrinsic [ILD/CED] are discussed.Editorial responsibility: J. Hoefs
S. S. MatsyukEmail:
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18.
Summary Sonoraite, FeTeO3(OH)·H2O, is monoclinic,P 21/c, witha=10.984(2),b=10.268(2),c=7.917(2) Å, =108.49(2)°. For 8 formula units per cell the calculated density is 4.179(2) g/cm3; the observed value is 3.95(1) g/cm3. The Supper-Pace automated diffractometer was used to collect 1884 independent reflections which were corrected for absorption. The structure was determined by an automated symbolic addition procedure. It was refined to a residualR of 6.2% using anisotropic temperature factors for the cations and isotropic temperature factors for the oxygen atoms. Chains of octahedra about Fe extend along [101]; edge-sharing pairs of these octahedra are joined by corner sharing. The Fe–Fe distances across the shared edges are 3.05 and 3.20 Å, short enough to suggest magnetic interactions. All but one H2O are involved in the chains. The Te4+ ions have a pseudotetrahedral coordination, with three oxygen ions forming one face of the tetrahedron and the lone electron pair of Te occupying the fourth corner. The O–Te–O average bond angle is 95°. The Fe chains are tied together by Te–O bonds in all three dimensions.
Die Kristallstruktur von Sonorait, Fe3+Te4+O3(OH).H2O
Zusammenfassung Sonorait, FeTeO3(OH)·H2O, ist monoklin, P 21/c, mit den folgenden Zelldimensionen:a=10,984(2),b=10,268(2),c=7,917(2) Å, =108,49(2)°. Mit 8 Formel-Einheiten errechnet man eine Dichte von 4,179(2) g/cm3; die gemessene Dichte beträgt 3,95(1) g/cm3. Das Supper-Pace automatische Diffraktometer wurde zur Sammlung von 1884 unabhängigen Reflexen benutzt, welche für Absorption korrigiert wurden. Die Struktur wurde mit Hilfe eines vollständig automatischen Programms für symbolische Addition bestimmt. Mit anisotropen Temperaturfaktoren für die Kationen und mit isotropen Temperaturfaktoren für die Sauerstoff-Atome wurde ein Residuum von 6,2% erreicht. Ketten von Eisen-Oktaedern erstrecken sich entlang [101]; Oktaeder-Paare mit gemeinsamen Kanten sind über Eckenverknüpfung verbunden. Die Fe–Fe-Abstände über die gemeinsamen Kanten betragen 3,05 und 3,20 Å, kurz genug, um zu magnetischer Wechselwirkung führen zu können. Nur ein H2O-Molekül ist nicht Teil einer Kette. Die Te4+-Ionen befinden sich in pseudotetraedrischer Koordination; drei Sauerstoff-Ionen bilden eine Fläche des Tetraeders, die vierte Ecke wird durch das einsame Elektronenpaar von Te besetzt. Der Mittelwert des O–Te–O-Bindungswinkels beträgt 95° Die Fe-Ketten werden durch Te–O-Bindungen dreidimensional verbunden.

With 3 Figures  相似文献   

19.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

20.
Summary The structure type of joaquinite has been derived from precession photographs (Mo radiation) of a polysynthetic twin. Space group: C 2/m; lattice constants:a=10.50Å,b=9.58Å;c=11.78Å;=109°32;cell content: Ba4Fe2RE4Ti4O4[Si4O12]4.The atomic arrangement was determined by Patterson-, Fourier-, and (F0–Fc)-syntheses. The least squares refinement (with isotropic temperature factors) led toR=0.16. The authors are of the opinion that this relativeley highR-value is due to the poor quality of the crystal.The main structural feature are double layers of [Si4O12]-rings parallel to (001) which are connected by 10-coordinated Ba and octahedrally coordinated Ti. These double layers have pseudo-symmetry C mmm, with mirror planes perpendicular toa, b, andc *. They are stacked alongc * and translated –3/8a. The orthorhombic pseudo-symmetry allows also the translation +3/8a which is responsible for both the formation of twins and the frequent stacking disorder. The described double layers are connected by 7-coordinated RE and 4-coordinated Fe.The rôles of Fe, which has an occupancy of only 1/2, and of Na and OH. which are reported in published analyses, are discussed.
Der Strukturtyp von Joaquinit
Zusammenfassung Der Strukturtyp von Joaquinit wurde aus Präzessionsaufnahmen (MoStrlg.) eines polysynthetischen Zwillings abgeleitet. Raumgruppe: C 2/m; Gitterkonstanten:a=10,50Å;b=9,58Å,c=11,78Å; =109°32, Zellinhalt: Ba4Fe2SE4Ti4O4[Si4O12]4.Die Atomanordnung wurde aus Patterson-, Fourier- und (F0–Fc)-Synthesen abgeleitet. Die Verfeinerung mit der Methode der Kleinsten Quadrate führte (mit isotropen Temperaturfaktoren) aufR=0,16. Die Autoren sind der Ansicht, daß dieser relativ hoheR-Wert von der schlechten Qualität des Kristalles herrührt.Wesentliches Strukturmotiv sind Doppelschichten von [Si4O12]-Ringen parallel (001), die durch 10-koordiniertes Ba und oktaedrisch koordiniertes Ti verknüpft werden. Diese Doppelschichten haben die Pseudosymmetrie C mmm mit Symmetrieebenen senkrechta, b undc *. Sie werden nachc * gestapelt und um –3/8a translatiert. Die rhombische Pseudosymmetrie läßt andererseits die Translation +3a zu, was für die Zwilligsbildung und die häufige Stapelungsunordnung verantwortlich ist. Diese Doppelschichten werden weiter durch 7-koordinierte SE und 4-koordinertes Fe verknüpft.Die Rollen des Fe, welches eine Punktlage nur zur Hälfte besetzt, und des Na und OH, welche in publizierten Analysen angegeben werden, werden diskutiert.

Mit 10 Abbildungen  相似文献   

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