The adsorption of olefins at 25 °C in gas- or vapor-solid systems on 4 clays dried at 120 °C was studied by infrared spectroscopy. Products of condensation have the spectra of paraffinic oligomers. Paraffins are adsorbed onto the same structural surface hydroxyls that adsorb olefins, confirming the physical unspecific character of this adsorption. These hydroxyls do not participate in the condensation reaction. The reappearance of these hydroxyl bands after evacuation suggests that product molecules are not adsorbed onto the surface but remain on it because of its low vapor pressure. The reversible adsorption sites participate in feeding the condensation sites. Double-bond isomerization of olefins was not observed, at room temperature, on clays, alumina and silicas dried at 120 °C. When the gas-phase is evacuated or swept with inert gas, reaction does not proceed with a new monomer. Paraffins are only physically adsorbed.

KCl-, KBr-, and KI-kaolinite intercalation complexes were synthesized by gradually heating potassium-halide discs of the dimethylsulfoxide (DMSO)-kaolinite intermediate at temperatures to 330°C. Two types of complexes were identified by infrared spectroscopy: almost non-hydrous, obtained during thermal treatment of the DMSO complex; and hydrated, produced by regrinding the disc in air. The former showed basal spacings with integral series of 00l reflections indicating ordered stacking of parallel 1:1 layers. Grinding resulted in delamination and formation of a disordered “card-house” type structure. The frequencies of the kaolinite OH bands show that the strength of the hydrogen bond between the intercalated halide and the inner-surface hydroxyl group decreases as Cl > Br > I. The positions of the H2O bands imply that halide-H2O interaction decreases in the same order. Consequently, the strength of the hydrogen bond between H2O and the oxygen atom plane increases in the opposite sequence.

In the non-hydrous KCl-kaolinite complex the inner hydroxyl band of kaolinite at 3620 cm-1 is replaced by a new feature at 3562 cm-1, indicating that these OH groups are perturbed. It is suggested that Cl ions penetrate through the ditrigonal hole and form hydrogen bonds with the inner OH groups. In contrast, Br and I ions are too large to pass into the ditrigonal holes and do not form hydrogen bonds with the inner hydroxyls.

Ferruginous beidellites with Al:Fe atomic ratios up to 2.36 were obtained when solutions containing Al, Fe2+ and H4SiO4 were adjusted to pH 8.5 with Ca(OH)2 and incubated at 95 °C in the presence of CaCO3 as a pH buffer. Incubation took place under cyclic reducing and oxidizing conditions achieved by adding 2 mM hydrazine at 14–15-d intervals over a period of 10–13 weeks. During the 14–15-d cycle, atmospheric oxygen slowly diffused through the high-density polyethylene bottles used, causing a slow oxidation of Fe(II) to Fe(III). The infrared (IR) spectra of the products approached that of natural beidellite, but indicated little change in octahedral Al:Fe ratio in the products for starting Al:Fe ratios from 2.5 up to 3.5, which was the highest Al:Fe ratio at which a well-crystallized product was obtained. Chemical analysis showed the presence of more Al+Fe in the products than could be incorporated into a dioctahedral formula. After the excess was assigned to a hydroxy-aluminium interlayer, the formula of the most Al-rich beidellite was calculated to be 0.575Ca(Si6.85A1.15)(Al2.47Fe1.53)O20(OH)4. This composition lay within the range recorded for the ferruginous beidellites that form in Vertisols.

The Mössbauer and infrared spectra of Li- and Rb-saturated nontronites from Washington, USA (SWa-1), heat treated at different temperatures, were measured. The Mössbauer results show that diffusion of Li+ into the 2:1 layer by heat treatment at 250-300°C does not affect the magnetic hyperfine interactions of the octahedral iron centers. In contrast, significant changes were observed by calcination at temperatures >300°C for Li-saturated nontronites. The main features of the Mössbauer spectra recorded at different temperatures reveal superparamagnetic behavior with a blocking temperature of ~5 K. The superparamagnetic behavior is related to small magnetic domains created by partially broken Fe-O-Fe bonds upon heat treatment. The infrared spectra of Li-rich nontronite, heat treated at 300°C, show changes attributed to Li migration into the hexagonal cavities. Heating to higher temperatures, produced changes in the spectra of the Li- and Rb-saturated nontronites owing to the dehydroxylation of the layer structure. The dehydroxylation process begins with the loss of OH groups in the FeOHFe bridges and is completed with the disruption of the Al-O bonds at >600°C.

To provide fundamental knowledge for studying the relative content of vacant sites and exploring the mechanism of interaction between Pb2+ and birnessite, Fourier transform infrared spectroscopy (FTIR) of birnessites with different Mn average oxidation states (AOS) before and after Pb2+ adsorption were investigated. The number of absorption bands of FTIR spectra was determined by using the second derivatives of the original spectra. The band at 899–920 cm–1 was assigned to the bending vibration of -OH located at vacancies. The bands at 1059–1070, 1115–1124 and 1165–1171 cm–1 could be attributed to the vibrations of Mn(III)-OH in MnO6 layers, and the intensities of these bands increased with decreasing Mn AOS. The bands at 990 and 1023–1027 cm–1 were ascribed to the vibrations of Mn(III)-OH in the interlayers. Mn(III) in MnO6 layers partially migrated to interlayers during Pb2+ adsorption, which led to an increased intensity of the band at 990 cm–1. The band at 564–567cm–1 was assigned to the vibration of Mn-O located at vacancies. This band could split by coupling of vibrations due to Pb2+ and/or Mn2+ adsorbed at vacant sites. The large distance between the band at 610–626 cm–1 and that at 638–659 cm–1 might reflect small Mn(III) ions located in Mn(III)-rich rows.

Arhbarite was described in 1982 as a new copper arsenate, Cu2(OH)AsO4·6H2O, from the Arhbar mine, Morocco. Due to the very small grain size no crystallographic data other than the X-ray powder diffraction data could be given. Reinvestigation of the type material and of new finds from the El Guanaco mine, Chile, is based on Rietveld refinement of X-ray powder data, electron microprobe investigations, optical studies as well as infrared and Raman spectra. The main results are: (1) arhbarite has the ideal formula Cu2Mg(AsO4)(OH)3 with magnesium oxide as an additional constituent and (2) arhbarite is isotypic with gilmarite, Cu3(AsO4)(OH)3. Arhbarite is triclinic, space group P1 (no. 1), unit-cell parameters (type material; refined from powder data) a= 5.315(4), b= 5.978(6), c= 5.030(6)Å, α = 113.58(6), β = 97.14(7), γ = 89.30(8)°, V= 145.2(1)Å3, Z= 1. Microprobe analyses of the type material gave MgO 10.20, CuO 47.46, NiO 0.20, CoO 0.24, As2O5 33.85, SiO2 0.10, H2O 7.58 (calc.), total 99.63 wt.%. The empirical formula is Cu1.98(Mg0.88Cu0.09Ni0.01Co0.01)S0.99(AsO4)1.02(OH)2.92, based on 7 O atoms. The Chilean arhbarite shows a slightly higher Cu content than the type material; it has the formula Cu1.99(Mg0.73Cu0.25Zn0.01)∑0.99[(AsO4)1.01(SiO4)0.01]∑1.02(OH)2.92. The formal redefinition of arhbarite has been approved by the CNMMN of the IMA.

Chernikovite and meta-ankoleite were synthesized with a relatively high crystallinity and the compounds were identified by means of chemical analysis and X-ray diffraction. The infrared spectra were recorded and the bands assigned. From the luminescence spectra, the band-gap energy for both compounds was calculated as 2.35 eV, indicating that they must be considered as insulators. The dependence of the solubilities of these compounds on the acidity of the solution was studied, and the dominant ionic species were determined. The pKsp values of chernikovite and meta-ankoleite were found to be 22.73±0.24 and 24.30±0.81 respectively.

Comparison of the infrared spectra of georgeite and a phase which can be reproducibily synthesised in the laboratory shows that the mineral is an amorphous analogue of malachite, Cu2CO3(OH)2. Synthetic studies also explain the chemical conditions under which georgeite may form, as well as those which can cause it to react to either malachite or chalconatronite. Parallels may be drawn between the laboratory observations and known mineral associations of georgeite.

Rappoldite, the Co-analogue of helmutwinklerite, and zincgartrellite, the Zn-dominant analogue of gartrellite, are two new members of the tsumcorite group. Both minerals are triclinic, their structures are closely related to the parent structure, i.e. the ‘tsumcorite type’ (C2/m, Z = 2). The lower symmetry is caused by two different crystal-chemical requirements. Order phenomena of the hydrogen bonds cause the ‘helmutwinklerite type’ (P1̄, Z= 4), ordering of Cu2+and Fe3+ is responsible for the ‘gartrellite type’ (P1̄, Z = 1).

Rappoldite was found on samples from the Rappold mine near Schneeberg, Saxony, Germany. The new species forms red to red-brown prismatic and tabular crystals up to 1 mm long. Dcalc. = 5.28 g/cm3. 2Vz = 85(5)°, nx = 1.85 (calc.), ny = 1.87(2) and nz = 1.90(2); dispersion is distinct with r > v; orientation is Y ∼∥ [1̄ 20] and X ∼ ∥ c. The empirical formula derived from electron microprobe analyses is (Pb1.01Ca0.01)Σ1.02(Co0.99Ni0.62Zn0.35Fe0.02)Σ1.98[(AsO4)1.99(SO4)0.01]Σ2.00[(OH)0.02(H2O)1.98]Σ2.00 or Pb(Co,Ni)2(AsO4)2·2H2O. Single-crystal X-ray studies showed average C2/m symmetry. Weak superstructure reflections are responsible for triclinic symmetry and enlarged cell metrics (refined from powder data): a= 11.190(2)Å, b= 10.548(2)Å, c= 7.593(1)Å, α = 100.38(1)8, β = 109.59(2)8, γ = 98.96(1)8, V= 807.6 Å3, Z= 4. The superstructure results from the hydrogen-bond scheme, but faint streaks indicate some disorder. All investigated rappoldite crystals are twinned by reflection on (23̄0) which corresponds to the mirror plane of the average C2/m cell. Helmutwinklerite is isotypic with rappoldite and probably also with pure thometzekite; sulphatian thometzekite is monoclinic.

Zincgartrellite forms green-yellow rosette-like aggregates on samples from the Tsumeb mine, Namibia. The Dcalc. = 5.30 g/cm3. 2Vx = 87(5)°, nx = 1.91(2), ny = 1.94 (calc.) and nz = 1.97(2). Electron-microprobe analyses and Mössbauer data yielded the empirical formula (Pb0.97Ca0.04)Σ1.01(Zn0.91Cu0.51Fe0.59Al0.03)Σ2.04[(AsO4)1.96(SO4)0.01]Σ1.97[(OH)0.81(H2O)1.31]Σ2.12 or Pb(Zn,Fe,Cu)2(AsO4)2(H2O,OH)2. The structural formula is Pb(ZnxFe1–x)(ZnxCu1–x)(AsO4)2(OH)1–x(H2O)1+xwith 0.4 < x < 0.8. Gartrellite is defined by x < 0.4. Helmutwinklerite has x near to 1 and is defined by a cell with fourfold volume. Single-crystal X-ray studies of zincgartrellite proved space group P1̄ caused by ordering of Fe3+ and Cu at one atomic site. Cell parameters (refined from powder data): a= 5.550(1)Å, b= 5.620(1)Å, c= 7.621(1)Å, α = 68.59(1), β = 69.17(1), γ = 69.51(1)°, V= 200.1 Å3, Z= 1.

Copiapite is a mineral of iron- and sulphate-rich acidic environments and has a general formula AFe3+4 (SO4)6(OH)2(H2O)20, where A = Fe2+, 2/3Fe3+, 2/3Al3+, Mg, Zn. The structure is built by infinite tetrahedral-octahedral chains and isolated octahedrally coordinated A sites. Our synthetic and natural copiapite samples can be divided into two large groups based on the orientation of the structural fragments. One group comprises copiapite phases where A = Al3+, Fe2+ or Fe3+ and we designate it as the structural type AL. The other group consists of copiapite with A = Mg2+, Zn2+ or Ni2+ and this is the structural type MG. The solid-solution series between Fe3+ and Al3+ copiapite is continuous. The series between Mg2+-Al3+, Mg2+-Fe3+ and Mg2+-Al3+-Fe3+ copiapite are not continuous; the samples with intermediate compositions contain two copiapite phases, one of the type AL and one of the type MG. The series between Mg2+ and Zn2+ copiapite is continuous only at 25°C. At 75°C, the Zn-rich portion of this systemcrystallizes a copiapite-like phase whose structure may be a superstructure of copiapite. The series between Al-Fe2+ and Mg-Fe2+ copiapite are not continuous and show complex behaviour of the intermediate compositions.

The physical behaviour of methane and carbon dioxide clathrate hydrates, specific crystallographic ice crystals are of major importance for the earth and may control the stability of gases in many astrophysical bodies such as the planets, comets and possibly interstellar grains. Such models claim they provide an alternative trapping mechanism modifying the absolute and relative composition of icy bodies and can be at the source of late time injection of gaseous species in planetary atmospheres. However, there is a clear need to detect them directly. We provide in this study the laboratory recorded signatures of clathrate hydrates in the near to mid-infrared for astrophysical remote detection. These laboratory experiments will in a near future allow to follow the kinetic formation by diffusion in dedicated experiments, another important step to implement, to understand and model their possible presence in space.

This study was motivated by the fact that some amino acids are currently identified in carbonaceous chondrites but none are yet observed in the interstellar medium. The question of the relative stability of these prebiotic compounds with respect to the other possible species of the same chemical formula is addressed by means of quantum chemical simulations based on density functional theory (DFT). A preliminary investigation of molecules with the formula C2H5O2N shows that glycine (H2NCH2COOH) is not the most stable compound that can be formed: it is ~10 kcal mol−1 higher in energy than CH3NHCOOH, which becomes the most likely candidate for a search in space. The same argument of relative stability used to explained why formamide H2N-HC=O was identified in the interstellar medium (rather than any of its isomers) provides here a rationalization of the permanent debate about the detection of glycine. A second investigation of protonated derivatives of the same series that may result from ion molecule chemistry shows that under its nitrogen protonated form (H3N+CH2COOH) glycine does become the most stable compound. This suggests that, if glycine presently detected in chondrites has an interstellar origin, it must have been synthetized as its protonated form by ion–molecule processes. A similar study was carried out on the corresponding glycine N-carboxyanhydride. The calculated rotational constants (GHz) of glycine A=10.3603; B=3.8590; C=2.9037 (Exp: 10.3418; 3.8762; 2.9123, respectively) served as the benchmark to derive the correcting factors necessary to estimate the rotational constants of the possible candidates within a few tenths of a percent. The dipole moments were determined and the values in the range 4–6 Debye obtained for the protonated species should be large enough to initiate laboratory experiments and/or observations. Theoretical infrared spectra are also provided to assist in the identification of these exotic species.

This paper looks at the possibility that the peptide bond may be more common than originally thought, leading to molecules of prebiotic interest containing heavier atoms of the second row of the periodic table. Ab initio Möller–Plesset (MP2) coupled-cluster molecular orbital methods and density functional theory have been used. A first investigation of the six-atom system [C,3H,O,N] showed that formamide, NH2[bond]CH[double bond]O, is the most stable system that can be formed. Systematic studies on this same system in which C, O and N were respectively replaced by Si, S and P were then carried out. It has been found that the peptide-like linkage is the most stable for [C,3H,S,N] and [Si,3H,O,N] where NH2[bond]CH[double bond]S and NH2[bond]SiH[double bond]O are about 10–14 kcal mol−1 more favourable than the corresponding enol tautomers and well below other isomers on the energy scale. For [C,3H,O,P], the most stable species is CH3[bond]P[double bond]O, which is found 18 kcal mol−1 below the PH2[bond]CH[double bond]O peptide analogue. By correcting the known inadequacies in the calculations with the average theoretical to experimental ratio from the benchmark molecules of the system, it is possible to obtain a best estimate of rotational constants and infrared frequencies that should be precise enough to initiate laboratory experiments and/or observations. The corrected values of B=6.0342 GHz and C=5.4921 GHz for NH2[bond]CH[double bond]S; B=9.2292 GHz and C=6.1164 GHz for NH2[bond]SiH[double bond]O; B=8.0275 GHz and C=6.4779 GHz for CH3[bond]P[double bond]O should be accurate to within a few tenths of a per cent. Theoretical infrared spectra are also provided to assist in identification of these exotic species.

The Fourier-transform infrared spectra and the electronic spectra of a series of petroleum fractions of different composition and origins have been studied. Furthermore, these fractions have been modified through the Scholl reaction, a reaction that causes an increase in the aromatic content of the fractions by causing the formation of polycyclic aromatic hydrocarbons (PAHs) or larger PAHs if they were already present in the pristine samples. It is shown that some heavily aromatic petroleum fractions are able to match the emission spectra of the protoplanetary nebula IRAS 22272+5435. Additionally, it is shown that the modified petroleum fractions are able to match the infrared spectrum of anthracite, a high-rank type of coal that has been proposed as the material responsible for the emission of the unidentified infrared bands (UIBs), but which can also be thought of as a model of the kerogen found in meteorites or assumed to be present in cometary nuclei. It is shown that the petroleum fractions considered in this work can be considered even better candidates than coal as a model for the matter present in protoplanetary nebulae and the carrier of the UIBs.

In this work we started from the basic idea that the pure polycyclic aromatic hydrocarbons (PAHs) cannot be the real carriers of the unidentified infrared bands (UIBs), the emission spectra coming from a large variety of astronomical objects. Instead we propose a new model taken from petroleum chemistry which, we can show, is able to match both the UIBs and even the protoplanetary nebulae (PPNe) spectra. PAHs such as phenanthrene, benzoperylene, coronene and pentacene, are too pure and too specific to really exist in the interstellar medium. Instead our model proposes that the carrier of UIBs and PPNe are complex molecular mixtures like those obtained as fractions during the petroleum refining processes. These molecular mixtures are so complex that practically the investigators did not try to identify each individual component but characterized the mixture with an average molecular structure that takes into account both the average molecular weight and the average content of aromatic, naphtenic (cycloaliphatic) and aliphatic (paraffinic) fraction. We show by infrared spectroscopy that petroleum fractions obtained at certain steps of the refining process are able to match the UIBs and the PPNe infrared bands with the advantage of not being so specific as PAHs are. Namely we have used as samples a distillate aromatic extract (DAE) a treated residual aromatic extract (T-RAE) and finally a naphtenic oil. Among the three samples examined, the DAE sample was the best in matching the UIBs and PPNe spectra.