Characterisation of organoclays and adsorption of p-nitrophenol : environmental application

Organoclays were synthesised through ion exchange of a single surfactant for sodium ions, and characterised by a range of method including X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM). The change in surface properties of montmorillonite and organoclays intercalated with the surfactant, tetradecyltrimethylammonium bromide (TDTMA) were determined using XRD through the change in basal spacing and the expansion occurred by the adsorbed p-nitrophenol. The changes of interlayer spacing were observed in TEM. In addition, the surface measurement such as specific surface area and pore volume was measured and calculated using BET method, this suggested the loaded surfactant is highly important to determine the sorption mechanism onto organoclays. The collected results of XPS provided the chemical composition of montmorillonite and organoclays, and the high-resolution XPS spectra offered the chemical states of prepared organoclays with binding energy. Using TGA and FT-IR, the confirmation of intercalated surfactant was investigated. The collected data from various techniques enable an understanding of the changes in structure and surface properties. This study is of importance to provide mechanisms for the adsorption of organic molecules, especially in contaminated environmental sites and polluted waters.

Thermal stability of the soil minerals destinezite and diadochite Fe3+2(PO4)(SO4)(OH)·6H2O - implications for soils in bush fires

Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the soil minerals destinezite and diadochite. These two minerals are identical except for their morphology. Diadochite is amorphous whereas destinezite is crystalline. Both minerals are found in soils. It is important to understand the stability of these minerals because soils are subject to bush fires especially in Australia. The thermal analysis patterns of the two minerals are similar but not identical. Subtle differences are observed in the DTG patterns. For destinezite, two DTG peaks are observed at 129 and 182°C attributed to the loss of hydration water, whereas only a broad peak with maximum at 84°C is observed for diadochite. Higher temperature mass losses at 685°C for destinezite and 655°C for diadochite, based upon the ion current curves, are due to sulphate decomposition. This research has shown that at low temperatures the minerals are stable but at high temperatures, as might be experienced in a bush fire, the minerals decompose.

Thermal stability of the ‘cave’ mineral brushite CaHPO4•2H2O -mechanism of formation and decomposition

Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the ‘cave’ mineral brushite. X-ray diffraction shows that brushite from the Jenolan Caves is very pure. Thermogravimetric analysis coupled with ion current mass spectrometry shows a mass loss at 111°C due to loss of water of hydration. A further decomposition step occurs at 190°C with the conversion of hydrogen phosphate to a mixture of calcium ortho-phosphate and calcium pyrophosphate. TG-DTG shows the mineral is not stable above 111°C. A mechanism for the formation of brushite on calcite surfaces is proposed, and this mechanism has relevance to the formation of brushite in urinary tracts.

The application of Raman spectroscopy to the study of the uranyl mineral coconinoite Fe2Al2(UO2)2(PO4)4(SO4)(OH)2•20H2O

Raman spectra of the uranyl containing mineral coconinoite, Fe2Al2(UO2)2(PO4)4(SO4)(OH)2•20H2O, are presented and compared with the mineral’s infrared spectra. Bands connected with (UO2)2+, (PO4)3- , (SO4)2-, (OH)- and H2O stretching and bending vibrations, are assigned. Approximate U-O bond lengths in uranyl, (UO2)2+, and O-H...O hydrogen bond lengths are calculated from the wavenumbers of the U-O stretching vibrations and (OH)- and H2O stretching vibrations, respectively, and compared with published data for similar natural and synthetic compounds.

A vibrational spectroscopic study of hydrated Fe3+ hydroxyl-sulphates; polymorphic minerals butlerite and parabutlerite

Raman and infrared spectra of two polymorphous minerals with the chemical formula Fe3+(SO4)(OH)•2H2O, monoclinic butlerite and orthorhombic parabutlerite, are studied and the spectra assigned. Observed bands are attributed to the (SO4)2- stretching and bending vibrations, hydrogen bonded water molecules, stretching and bending vibrations of hydroxyl ions, water librational modes, Fe-O and Fe-OH stretching vibrations, Fe-OH bending vibrations and lattice vibrations. The O-H...O hydrogen bond lengths in the structures of both minerals are calculated from the wavenumbers of the stretching vibrations. One symmetrically distinct (SO4)2- unit in the structure of butlerite and two symmetrically distinct (SO4)2- units in the structure of parabutlerite are inferred from the Raman and infrared spectra. This conclusion agrees with the published crystal structures of both mineral phases.

Raman spectroscopy of newberyite Mg(PO3OH)•3H2O – a cave mineral

Newberyite Mg(PO3OH)•3H2O is a mineral found in caves such as from Moorba cave, Jurien Bay, Western Australia, the Skipton Lava tubes (SW of Ballarat, Victoria, Australia) and in the Petrogale Cave (Madura , Eucla, Western Australia). Because these minerals contain oxyanions, hydroxyl units and water, the minerals lend themselves to spectroscopic analysis. Raman spectroscopy can investigate the complex paragenetic relationships existing between a number of ‘cave’ minerals. The intense sharp band at 982 cm-1 is assigned to the PO43- ν1 symmetric stretching mode. Low intensity Raman bands at 1152, 1263 and 1277 cm-1 are assigned to the PO43- ν3 antisymmetric stretching vibrations. Raman bands at 497 and 552 cm-1 are attributed to the PO43- ν4 bending modes. An intense Raman band for newberyite at 398 cm-1 with a shoulder band at 413 cm-1 is assigned to the PO43- ν2 bending modes. The values for the OH stretching vibrations provide hydrogen bond distances of 2.728Å (3267 cm-1), 2.781Å (3374cm-1), 2.868Å (3479 cm-1), and 2.918Å (3515 cm-1). Such hydrogen bond distances are typical of secondary minerals. Estimates of the hydrogen-bond distances have been made from the position of the OH stretching vibrations and show a wide range in both strong and weak bonds.

Raman spectroscopy of stercorite H(NH4)Na(PO4)•4H2O – a cave mineral from Petrogale Cave, Madura, Eucla, Western Australia

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the mineral stercorite H(NH4)Na(PO4)·4H2O. The mineral stercorite originated from the Petrogale Cave, Madura, Eucla, Western Australia. This cave is one of many caves in the Nullarbor Plain in the South of Western Australia. These caves have been in existence for eons of time and have been dated at more than 550 million years old. The mineral is formed by the reaction of bat guano chemicals on calcite substrates. A single Raman band at 920 cm−1 defines the presence of phosphate in the mineral. Antisymmetric stretching bands are observed in the infrared spectrum at 1052, 1097, 1135 and 1173 cm−1. Raman spectroscopy shows the mineral is based upon the phosphate anion and not the hydrogen phosphate anion. Raman and infrared bands are found and assigned to PO43−, H2O, OH and NH stretching vibrations. The detection of stercorite by Raman spectroscopy shows that the mineral can be readily determined; as such the application of a portable Raman spectrometer in a ‘cave’ situation enables the detection of minerals, some of which may remain to be identified.

Raman spectroscopic study of the minerals diadochite and destinezite Fe3+2(PO4,SO4)2(OH)•6H2O – implications for soil science

The two minerals diadochite and destinezite of formula Fe2(PO4,SO4)2(OH)•6H2O have been characterised by Raman spectroscopy and complimented with infrared spectroscopy. These two minerals are both found in soils and are identical except for their morphology. Diadochite is amorphous whereas destinezite is highly crystalline. The spectra of diadochite are broad and ill-defined, whereas the spectra of destinezite are intense and well defined. Bands are assigned to phosphate and sulphate stretching and bending modes. Two symmetric stretching modes for both the phosphate and sulphate symmetric stretching modes support the concept of non-equivalent phosphate and sulphate units in the mineral structure. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths.

Halogen bonding between an isoindoline nitroxide and 1,4-diiodotetrafluorobenzene: new tools and tectons for self-assembling organic spin systems

Halogen bonding has been observed for the first time between an isoindoline nitroxide and an iodoperfluorocarbon (see figure), which cocrystallize to form a discrete 2:1 supramolecular compound in which NO.⋅⋅⋅I halogen bonding is the dominant intermolecular interaction. This illustrates the potential use of halogen bonding and isoindoline nitroxide tectons for the assembly of organic spin systems...