Raman spectroscopy of hydrogen arsenate group (AsO3OH)2− in solid-state compounds: cobalt-containing zinc arsenate mineral, koritnigite (Zn,Co)(AsO3OH)·H2O

Raman spectra of two well-defined types of koritnigite crystals from the Jáchymov ore district, Czech Republic, were recorded and interpreted. No substantial differences were observed between both crystal types. Observed Raman bands were attributed to the (AsO3OH)2- stretching and bending vibrations, stretching and bending vibrations of water molecules and hydroxyl ions. Non-interpreted Raman spectra of koritnigite from the RRUFF database, and published infrared spectra of cobaltkoritnigite were used for comparison. The O-H...O hydrogen bond lengths in the crystal structure of koritnigite were inferred from the Raman spectra and compared with those derived from the X-ray single crystal refinement. The presence of (AsO3OH)2- units in the crystal structure of koritnigite was proved from the Raman spectra which supports the conclusions of the X-ray structure analysis.

Thermal analysis and infrared emission spectroscopic study of kaolinite-potassium acetate intercalate complex

The thermal behavior and decomposition of kaolinite-potassium acetate intercalation complex was investigated through a combination of thermogravimetric analysis and infrared emission spectroscopy. Three main changes were observed at 48, 280, 323 and 460 °C which were attributed to (a) the loss of adsorbed water (b) loss of the water coordinated to acetate ion in the layer of kaolinite (c) loss of potassium acetate in the complex and (d) water through dehydroxylation. It is proposed that the KAc intercalation complex is stability except heating at above 300 °C. The infrared emission spectra clearly show the decomposition and dehydroxylation of the kaolinite intercalation complex when the temperature is raised. The dehydration of the intercalation complex is followed by the loss of intensity of the stretching vibration bands at region 3600-3200 cm-1. Dehydroxylation is followed by the decrease in intensity in the bands between 3695 and 3620 cm-1. Dehydration is completed by 400 °C and partial dehydroxylation by 650 °C. The inner hydroxyl group remained until around 700 °C.

Infrared spectroscopic study of halloysite-potassium acetate intercalation complex

Mid-infrared (MIR) and near-infrared (NIR) spectroscopy have been used to study the molecular structure of halloysite and potassium acetate intercalated halloysite and to determine the structural changes of halloysite through intercalation. The MIR spectra show all fundamental vibrations including the hydroxyl units, basic aluminosilicate framework and water molecules in the structure of halloysite and its intercalation complex. Comparison between halloysite and halloysite-potassium acetate intercalation complex shows almost all bands observed for halloysite are also observed for halloysite-potassium acetate intercalation complex apart from bands observed in the 1700-1300 cm-1 region, but with differences in band intensity. However, NIR, based on MIR spectra, provide sufficient evidence to analyze the structural changes of halloysite through intercalation. There are obvious differences between halloysite and halloysite-potassium acetate intercalation complex in the all spectral ranges. Therefore, the reproducibility of measurement and richness of qualitative information should be simultaneously considered for proper selection of a spectroscopic method for molecular structural analysis.

Synthesis and vibrational spectroscopy of halotrichite and bilinite

Near infrared (NIR), infrared (IR) spectroscopy and X-ray diffraction (XRD) have been applied to halotrichites of the formula FeAl2(SO4)4∙22H2O and Fe2+Fe23+(SO4)4∙22H2O. Comparison of the halotrichites and their starting materials has been used to give a better understanding of the bonding involved in these types of minerals. The vibrational spectroscopy data has shown that Fe2+ oxidises during the formation of halotrichite, no preventative measures were implemented to prevent oxidation, and this has been clearly shown by the position and broadness of electronic bands of transition metals in the NIR spectra (12500 to 7500 cm-1). It is apparent from this region that Fe3+ substitutes for Al3+ in the synthesis of halotrichite. Due to the oxidation of Fe2+ to Fe3+ the halotrichite sample contains a small portion of bilinite. This has been confirmed by XRD, peaks at 9 and 14° 2θ were observed in the halotrichite sample and are identical to the XRD pattern obtained for bilinite. Substitution of aluminium for Fe3+ has resulted in significant changes in the overall infrared and NIR spectral profiles. However, the lower wavenumber regions of the NIR spectra have very similar spectral profiles, which indicate a similar structure to halotrichite has formed for bilinite. This work has shown that iron halotrichites can be synthesised and characterised by infrared and NIR spectroscopy.

A Raman spectroscopic study of M2+M3+ sulfate minerals, römerite Fe2+Fe23+ (SO4)4· 14H2O and botryogen Mg2+Fe3+ (SO4)2(OH)·7H2O

The mixed valency (M2+M3+) sulphate minerals, römerite Fe2+Fe23+(SO4)4•14H2O and botryogen Mg2+Fe3+(SO4)2(OH).7H2O have been studied by Raman spectroscopy. The Raman spectra of the two types of crystals proved very similar but not identical. The observation of two symmetric stretching modes confirmed the presence of the two non-equivalent sulphate units in the römerite structure. The observation of multiple bands in the antisymmetric stretching region and in the bending regions proves the symmetry of the sulphate anion is significantly reduced in the römerite structure. The number of Raman bands related to the (SO4)2- symmetric and antisymmetric vibrations support the X-ray single crystal structure conclusion that two symmetrically distinct S6+ are present in the structure of botryogen. Römerite is a mineral of environmental significance as it is commonly found in tailings and dumps.

Raman spectroscopic study of the uranyl titanate mineral brannerite (U,Ca,Y,Ce)2(Ti,Fe)2O6 –Effect of Metamictization

Raman spectra of the uranyl titanate mineral brannerite were analysed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. Observed bands are attributed to the TiO and (UO2)2+ stretching and bending vibrations, U-OH bending vibrations, H2O and (OH)- stretching, bending and libration modes. U-O bond lengths in uranyls and O-H…O bond lengths are calculated from the wavenumbers assigned to the stretching vibrations. Raman bands of brannerite are in harmony with those of the uranyl oxyhydroxides. The mineral brannerite is metamict as is evidenced by the intensity of the UO stretching and bending modes being of lower intensity than expected and with bands that are significantly broader.

Single crystal Raman spectroscopy of natural leiteite ZnAs2O4 and in comparison with the synthesised mineral

The oriented single crystal Raman spectrum of leiteite has been obtained and the spectra related to the structure of the mineral. The intensities of the observed bands vary according to orientation allowing them to be assigned to either Ag or Bg modes. Ag bands are generally the most intense in the CAAC spectrum, followed by ACCA, CBBC, and ABBA whereas Bg bands are generally the most intense in the CBAC followed by ABCA. The CAAC and ACCA spectra are identical, as are those obtained in the CBBC and ABBA orientations. Both cross-polarised spectra are identical. Band assignments were made with respect to bridging and non-bridging As-O bonds.

Raman spectroscopy of gallium- and zinc-based hydrotalcites

Insight into the unique structure of hydrotalcites (HTs) has been obtained using Raman spectroscopy. Gallium-contg. HTs of formula Zn4 Ga2(CO3)(OH)12 · xH2O (2:1 ZnGa-HT), Zn6 Ga2(CO3)(OH)16 · xH2O (3:1 ZnGa-HT) and Zn8 Ga2(CO3)(OH)18 · xH2O (4:1 ZnGa-HT) have been successfully synthesized and characterised by X-ray diffraction (XRD) and Raman spectroscopy. The d(003) spacing varies from 7.62 Å for the 2:1 ZnGa-HT to 7.64 Å for the 3:1 ZnGa-HT. The 4:1 ZnGa-HT showed a decrease in the d(003) spacing, compared to the 2:1 and 3:1 compds. Raman spectroscopy complemented with selected IR data has been used to characterize the synthesized gallium-contg. HTs. Raman bands obsd. at around 1050, 1060 and 1067 cm-1 are attributed to the sym. stretching modes of the (CO32-) units. Multiple ν3 (CO32-) antisym. stretching modes are found between 1350 and 1520 cm-1, confirming multiple carbonate species in the HT structure. The splitting of this mode indicates that the carbonate anion is in a perturbed state. Raman bands obsd. at 710 and 717 cm-1 and assigned to the ν4 (CO32-) modes support the concept of multiple carbonate species in the interlayer.

A Raman spectroscopic study of copiapites Fe2+Fe3+(SO4)6(OH)2 · 20H2O: environmental implications

Raman spectroscopy has been used to study selected mineral samples of the copiapite group. Copiapite (Fe2+Fe3+(SO4)6(OH)2 · 20H2O) is a secondary mineral formed through the oxidn. of pyrite. Minerals of the copiapite group have the general formula AFe4(SO4)6(OH)2 · 20H2O, where A has a + 2 charge and can be either magnesium, iron, copper, calcium and/or zinc. The formula can also be B2/3Fe4(SO4)6(OH)2 · 20H2O, where B has a + 3 charge and may be either aluminum or iron. For each mineral, two Raman bands are obsd. at around 992 and 1029 cm-1, assigned to the (SO4)2-ν1 sym. stretching mode. The observation of two bands provides evidence for the existence of two non-equiv. sulfate anions in the mineral structure. Three Raman bands at 1112, 1142 and 1161 cm-1 are obsd. in the Raman spectrum of copiapites, indicating a redn. of symmetry of the sulfate anion in the copiapite structure. This redn. in symmetry is supported by multiple bands in the ν2 and ν4(SO4)2- spectral regions.

Single crystal Raman spectroscopy of brandholzite Mg[Sb(OH)6]2•6H2O and bottinoite Ni[Sb(OH)6]2•6H2O and the polycrystalline Raman spectrum of mopungite Na[Sb(OH)6]

The single crystal Raman spectra of minerals brandholzite and bottinoite, formula M[Sb(OH)6]2•6H2O, where M is Mg+2 and Ni+2 respectively, and the non-aligned Raman spectrum of mopungite, formula Na[Sb(OH)6], are presented for the first time. The mixed metal minerals comprise of alternating layers of [Sb(OH)6]-1 octahedra and mixed [M(H2O)6]+2 / [Sb(OH)6]-1 octahedra. Mopungite comprises hydrogen bonded layers of [Sb(OH)6]-1 octahedra linked within the layer by Na+ ions. The spectra of the three minerals were dominated by the Sb-O symmetric stretch of the [Sb(OH)6]-1 octahedron, which occurs at approximately 620 cm-1. The Raman spectrum of mopungite showed many similarities to spectra of the di-octahedral minerals informing the view that the Sb octahedra gave rise to most of the Raman bands observed, particularly below 1200 cm-1. Assignments have been proposed based on the spectral comparison between the minerals, prior literature and density field theory calculations of the vibrational spectra of the free [Sb(OH)6]-1 and [M(H2O)6]+2 octahedra by a model chemistry of B3LYP/6-31G(d) and lanl2dz for the Sb atom. The single crystal data spectra showed good mode separation, allowing the majority of the bands to be assigned a symmetry species of A or E.

Raman spectroscopic study of the uranyl titanate mineral euxenite (Y,Ca,U,Ce,Th) (Nb,Ta,Ti)2O6

Raman spectra of the uranyl titanate mineral euxenite were analyzed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. The obsd. bands are attributed to the Ti[n.63743]O and (UO2)2+ stretching and bending vibrations, as well as lattice vibrations of rare-earth ions. The Raman bands of euxenite are in harmony with those of the uranyl oxyhydroxides. The mineral euxenite is metamict as is evidenced by the intensity of the U[n.63743]O stretching and bending modes, which are of lower intensity than expected, and with bands that are significantly broader.

Synthesis and Raman spectroscopic characterisation of hydrotalcites based on the formula Ca6Al2(CO3)(OH)16· 4H2O

We have successfully synthesized hydrotalcites (HTs) contg. calcium, which are naturally occurring minerals. Insight into the unique structure of HTs has been obtained using a combination of X-ray diffraction (XRD) as well as IR and Raman spectroscopies. Calcium-contg. hydrotalcites (Ca-HTs) of the formula Ca4Al2(CO3)(OH)12·4H2O (2:1 Ca-HT) to Ca8Al2(CO3)(OH)20· 4H2O (4:1 Ca-HT) have been successfully synthesized and characterised by XRD and Raman spectroscopy. XRD has shown that 3:1 calcium HTs have the largest interlayer distance. Raman spectroscopy complemented with selected IR data has been used to characterize the synthesized Ca-HTs. The Raman bands obsd. at around 1086 and 1077 cm-1 were attributed to the ν1 sym. stretching modes of the (CO32-) units of calcite and carbonate intercalated into the HT interlayer. The corresponding ν3 CO32- antisym. stretching modes are found at around 1410 and 1475 cm-1.

Single-crystal Raman spectroscopy of natural schafarzikite FeSb2O4 from Pernek, Slovak Republic

The single crystal Raman spectra of natural mineral schafarzikite FeSb2O4 from the Pernek locality of the Slovak Republic are presented for the first time. Raman spectra of natural mineral apuanite Fe2+Fe43+Sb4O12S, originating from the Apuan Alps in Italy, as well as spectra of synthetic ZnSb2O4 and arsenite mineral trippkeite CuAs2O4 are also presented for the first time. The spectra of the antimonite minerals are characterized by a strong band in the region 660 – 680 cm-1 with shoulders on either side, and a band of medium intensity near 300 cm-1. The spectrum of the arsenite mineral is characterized by a medium band near 780 cm-1 with a shoulder on the high wavenumber side and a strong band at 370 cm-1. Assignments are proposed based on the spectral comparison between the compounds, symmetry modes of the bands and prior literature. The single crystal spectra of schafarzikite showed good mode separation, allowing bands to be assigned a symmetry species of A1g, B1g, B2g or Eg.

Thermal behavior and decomposition of kaolinite-potassium acetate intercalation composite

A series of kaolinite-potassium acetate intercalation composite was prepared. The thermal behavior and decomposition of these composites were investigated by simultaneous differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), X-ray diffraction (XRD) and Fourier-transformation infrared (FT-IR). The XRD pattern at room temperature indicated that intercalation of potassium acetate into kaolinite causes an increase of the basal spacing from 0.718 to 1.428nm. The peak intensity of the expanded phase of the composite decreased with heating above 300°C, and the basal spacing reduced to 1.19nm at 350°C and 0.718nm at 400°C. These were supported by DSC-TGA and FT-IR measurements, where the endothermic reactions are observed between 300 and 600°C. These reactions can be divided into two stages: 1) Removal of the intercalated molecules between 300-400°C. 2) Dehydroxylation of kaolinite between 400-600°C. Significant changes were observed in the infrared bands assigned to outer surface hydroxyl, inner surface hydroxyl, inner hydroxyl and hydrogen bands.

Vibrational spectroscopic study of the antimonate mineral bindheimite Pb2Sb2O6(O,OH)

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the antimonate mineral bindheimite Pb2Sb2O6(O,OH). The mineral is characterised by an intense Raman band at 656 cm-1 assigned to SbO stretching vibrations. Other lower intensity bands at 664, 749 and 814 cm-1 are also assigned to stretching vibrations. This observation suggests the non-equivalence of SbO units in the structure. Low intensity Raman bands at 293, 312 and 328 cm-1 are assigned to the OSbO bending vibrations. Infrared bands at 979, 1008, 1037 and 1058 cm-1 may be assigned to δ OH deformation modes of SbOH units. Infrared bands at 1603 and 1640 cm-1 are assigned to water bending vibrations, suggesting that water is involved in the bindheimite structure. Broad infrared bands centred upon 3250 cm-1 supports this concept. Thus the true formula of bindheimite is questioned and probably should be written as Pb2Sb2O6(O,OH,H2O)