Lixiviation of argillaceous rocks: Impact of oxidation degree states on organic compound mobilization

This work aims to study the influence of oxidation degree state which reached by organic matter included in argillaceous rocks on lixiviation and mobilization of compounds. Experimental lixiviation was carried out on two argillaceous rocks sampled in the surface deposit of the Andra laboratory (Bure, France). Molecular and spectroscopic characterizations of the organic matter extracts reveal two different oxidation levels reached by these samples: (i) a well preserved and (ii) an oxidized samples. Dissolved organic matter content and molecular investigation of sediment bitumen show that hydrophobic molecules (hydrocarbons) remain stable during lixiviation whereas specific polar compounds (alkanoic acids) are progressively removed by water. Moreover, occurrence of secondary alkanols with a molecular distribution similar to initial n-alkanes suggests that even in the well preserved sample, oxidation already occurs and that secondary alkanols can be used as specific markers for low intensity oxidation.     

Structural characterization of the δ-clathrate forms of syndiotactic polystyrene with n-alkanes

The δ-clathrate forms of syndiotactic polystyrene (s-PS) containing a homologous series of guests characterized by an increasing molecular volume (n-alkanes ranging from n-pentane to n-dodecane) have been investigated. The present analysis allows concluding that the volume of the guest plays a crucial role in the choice of the type of δ-clathrate that can be obtained. As a matter of fact, longer n-alkanes, such as n-octane, n-nonane or n-decane, turned out to give rise triclinic δ-clathrates presenting a guest/monomeric-unit ratio of 1/8, while δ-clathrates containing shorter alkanes, like n-hexane or n-heptane, instead, present a monoclinic or a triclinic structure with a guest/monomeric-unit ratio of 1/4. These results confirm the validity of a simple criterion to predict the type of s-PS δ-clathrate with a certain guest on the basis of the experimental d₀₁₀, as described in Macromolecules 2010, 43, 8549-8558. Moreover, our analysis confirms previous solid state ¹³C NMR and Raman spectroscopy data, indicating that shorter n-alkanes molecules, like n-hexane, are hosted in the cavities with an all-trans conformation while longer alkanes, like n-nonane, present bent conformations. The effect of n-alkanes molecules on the crystallization of s-PS amorphous samples has been investigated too.     

Structural behaviour of molecular alloys: n-pentacontane (n-C50H102)-n-pentacosane (n-C25H52); n-pentacontane (n-C50H102)-n-tricosane (n-C23H48) at room temperature

This paper displays a study of binary mixtures of n-alkanes whose ratio of chain length is around two. The systems composed of n-tricosane (n-C₂₃H₄₈)-n-pentacontane (n-C₅₀H₁₀₂) and n-pentacosane (n-C₂₅H₅₂)-n-pentacontane (n-C₅₀H₁₀₂) have been studied by means of X-ray analyses. These latter, performed at room temperature, showed in both cases, the existence of a large domain where the phases characteristic of each pure component coexist. These mixtures obey Kravchenko's rule relative to the solubility of the n-alkanes according to the chain length of each component. The mixtures studied do not form an intermediate solid solution. In other words, there is no particular arrangement of the shorter molecules inside the crystallographic unit of the longer.     

Structural information from progression bands in the FTIR spectra of long chain n-alkanes

The low temperature FTIR spectrum of long chain n-alkanes has been investigated in the region between the C-C stretching and CH₂ twisting fundamentals (1050-1133 cm⁻¹). With successive annealing and cooling stages, extended chain crystals of n-C₁₉₈H₃₉₈ show an improvement in the regularity of the progression bands observed. This is related to a ‘perfecting’ of the crystals. A once-folded sample of the same alkane shows additional features between 1050 and 1100 cm⁻¹, attributed to resonance modes from a tight (110) fold. These disappear on transformation to the extended form, to be replaced by progression bands. Assignment of the individual bands enables the length of the all-trans chain to be estimated and this method is used to show that centre-branched long chain n-alkanes have a folded conformation. It is also shown that the chain length derived from such FTIR data for a 1:1 molar mixture of n-C₁₆₂H₃₂₆ and n-C₂₄₆H₄₉₄ is consistent with a triple layer superlattice structure.     

Changes in the composition of the bituminous components of valley peat under stimulated microbial action

The stimulated microbial oxidation of valley peat by aboriginal microflora was experimentally studied for evaluating the participation of microflora in the conversion of organic matter in present-day swamp deposits. The esters of n-carboxylic acids, triphenyl phosphates, C₁₄–C₃₁ n-alkanes, squalene, methyldehydroabietate, steroids, and pentacyclic terpenoids with the predominance of unsaturated structures mainly with the alcohol groups were identified in the composition of the bituminous components of microflora. It was found that the absolute concentrations of all of the identified groups of organic compounds in peat considerably decreased as a result of biodegradation. The relative concentrations of high-molecularweight (C₂₇–C₃₄) homologues and C₁₆–C₂₀ homologues predominant in bacteria in the composition of peat n-alkanes increased. Steroids and pentacyclic triterpenoids were enriched in unsaturated structures and compounds with the alcohol groups. Aldehydes disappeared from the composition of acyclic compounds. The fractions of palmitic acid derivatives in methyl ethers and isoprenoid structures in alkanones sharply increased.     

Effect of chain-length of n-alkane on solvent-induced crystallization and solvent exchange phenomenon in syndiotactic polystyrene

The effect of molecular size and the vapor pressure of a series of n-alkanes as a solvent on solvent-induced crystallization of amorphous sPS and also the solvent exchange phenomenon in the δ form of syndiotactic polystyrene (sPS) were investigated by means of FT-IR spectroscopy and X-ray diffraction. The crystallization of amorphous sPS was found to be very much influenced by the molecular size and the vapor pressure of the n-alkanes used. At room temperature, n-alkanes with six and seven carbon atoms crystallize the sPS into the δ form, whereas the longer n-alkanes did not induce the crystallization of the amorphous sPS. By increasing the crystallization temperature to 50 °C, the vapor pressure of n-alkanes increases and as a result n-alkanes with eight to ten carbon atoms crystallize the amorphous sPS into the γ form unlike the cases of n-hexane and n-heptane. On further increasing the chain-length of n-alkanes to n-tridecane and n-hexadecane, no crystallization of amorphous sPS was observed even at 50 °C. By keeping the crystallization behavior in mind, we used these n-alkanes to exchange the existing solvent in the δ form of sPS/chloroform complex. n-Alkanes with six and seven carbon atoms easily replace the chloroform enclosed in the crystal lattice at room temperature and the d₀₁₀ lattice spacing was found to increase according to the molecular size of the solvent used in the exchange process. n-Alkanes with eight to ten carbon atoms could also replace the chloroform enclosed in the crystal lattice at room temperature. But in this case the d₀₁₀ lattice spacing was found to be similar or lower than that of the δ form of sPS/chloroform complex and a new reflection was observed 2θ = 6.6°, indicating the formation of the ? form. On the other hand, longer n-alkanes (C13 and C16) did not intrude into the cavities of the δ form at room temperature. By increasing the solvent exchange temperature to 50 °C, the longer n-alkanes (C13 and C16) also replaced the existing chloroform in the δ form and structure transformed to the ? form. In this way, we found that the crystallization and solvent exchange process of sPS using n-alkanes is quite complicated and depends strongly on the chain-length of n-alkane molecule.     

Simulations of the mobile phase of polyethylene

Results are presented from atomistic molecular dynamics simulations of the mobile pseudo-hexagonal phase of polyethylene, which occurs under conditions of elevated pressure and temperature. Three different types of model are considered, all of which employ periodic boundary conditions. The first model consists of n-alkane sequences (48×-C₂₄H₄₈-) that are bonded across the simulation box boundaries to produce chains that are effectively infinite in extent. On heating, at high pressure, this system displays a rotator phase, in which the chains retain an all-trans conformation, and rotate as semi-rigid units. A second model, consisting of finite n-alkanes (48×C₂₄H₅₀) displays the same behaviour at low temperatures, but at high temperature and pressure forms a conformationally disordered rotator phase, characterised by a large proportion of gauche defects and a significant lattice expansion. The final model considered contains long n-alkanes (24×C₁₀₂H₂₀₆) which contain jog defects and each pass twice through the simulation box. This model forms a conformationally disordered rotator phase at high temperature and ambient pressure. The behaviour of the three models, in terms of the variations in chain conformation and rotational and translational dynamics, are compared. The conformationally disordered phases provide useful representations of the experimentally observed mobile phase.     

Structural characterization of Saudi Arabian medium crude oil by n.m.r. spectroscopy

Saudi Arabian medium crude oil has been characterized by ¹H and ¹³C n.m.r. spectroscopy. Several structural parameters such as the percentage of aliphatic carbons, aromatic carbons, n-alkanes, naphthenes, branched alkanes and chain length of paraffinic chains were calculated. The aromatic carbons were further classified as those attached to a hydrogen, methyl or alkyl group, or bridgehead carbons.     

Comparative protective abilities of organothiols SAM coatings applied to copper dissolution in aqueous environments

Self-assembled monolayers (SAMs) obtained by adsorption of n-organothiols molecules have been formed onto polycrystalline copper surfaces in order to build up barrier films protecting copper from oxidation. In this context, formation of n-dodecanethiol (DT), (3-mercaptopropyl)trimethoxysilane (MPTS) and 11-perfluorobutylundecanethiol (F₄H₁₁) monolayers has been elaborated on copper and evaluated by X-ray photoelectron spectroscopy while polarization and cyclic voltammetry curves were used to compare the inhibition efficiency of the three organic coatings. Furthermore, atomic absorption spectrometry measurements were carried out in domestic water and in NaCl 0.5 M solutions in order to evaluate and quantify the dissolution of copper electrodes before and after protection. Results showed evidences that, among the three organic compounds assessed, F₄H₁₁ is the most suitable candidate to slow down the copper oxidation process.     

Non-premixed fluidized bed combustion of C1-C4n-alkanes

The non-premixed combustion of C₁-C₄n-alkanes with air was investigated inside a bubbling fluidized bed of inert sand particles at intermediate temperatures: 923 K ? T_B ? 1123 K. For ethane, propane and n-butane, combustion occurred mainly in the freeboard region at bed temperatures below T₁ = 923 K. On the other hand, complete conversion occurred within 0.2 m of the injector at: T₂ = 1073 K. For methane, the measured values of T₁ and T₂ were significantly higher at 1023 K and above 1123 K, respectively. The fluidized bed combustion was accurately modeled with first-order global kinetics and one PFR model to represent the main fluidized bed body. The measured global reaction rates for C₂-C₄n-alkanes were characterized by a uniform Arrhenius expression, while the global reaction rate for methane was significantly slower. Reactions in the injector region either led to significant conversion in that zone or an autoignition delay inside the main fluidized bed body. The conversion in the injector region increased with rising fluidized bed temperature and decreased with increasing jet velocity. To account for the promoting and inhibiting effects, an analogy was made with the concept of induction time: the PFR length (b_i) of the injector region was correlated to the fluidized bed temperature and jet velocity using an Arrhenius expression. These results show that the conversion of C₂-C₄n-alkanes can be estimated with one set of critical bed temperatures and modeled with one Arrhenius kinetics expression.     

Structure of Green River oil shale kerogen: Determination using solid state 13C n.m.r. spectroscopy

A sample of kerogen isolated from a Green River oil shale has been examined using high resolution solid state ¹³C n.m.r. spectroscopy. The relative concentrations of carbon types have been determined using a novel peak-synthesis technique applied to the ¹³C spectra. This technique has been successfully applied in determining the amount and type of individual carbon atoms in a sample of Green River oil shale kerogen, with sufficient resolution to enable an average structure to be proposed. The kerogen is highly aliphatic and appears to contain substantial quantities of both saturated polycondensed ring structures, and long chain n-alkanes or n-alkyl substituents.     

Hydrothermal alteration of sedimentary organic matter in the presence and absence of hydrogen to tar then oil

Hydrothermal alteration (hydrous pyrolysis) experiments, in the absence and presence of H₂ (reductive), were conducted on organic matter from marine and lacustrine sediments. The experiments were carried out at discrete temperatures from 150 °C to 350 °C to assess the yields and compositions of the bitumen (tar) formed and subsequently at higher temperatures the oil generated. The yield of bitumen was observed to increase with increasing temperatures. Under hydrous pyrolysis conditions with hydrogen, the yield increases by an order of magnitude and immature lacustrine organic matter shows the highest yield. Bitumen, the extractable organic matter at temperatures below 250-300 °C, contains mainly polar compounds, an unresolved complex mixture (UCM) of branched and cyclic compounds, with low amounts of saturated hydrocarbons. The polar compounds include n-alkanoic acids, n-alkanedioic acids, n-alkanols, isoprenoid ketones and methyl alkanoates. At temperatures above 300 °C, the bitumens transform into petroleum products with saturated hydrocarbons (n-alkanes and biomarkers) and UCM as the major components (>95% of total yield). The degree of maturation of the generated oil increases with increasing temperature under both pyrolysis conditions to full maturity at >350 °C. Although, the bitumen yield is much higher under conditions with added hydrogen, the maturity of the generated oil is lower than with just hydrous pyrolysis.     

Effect of aromatics and iso-alkanes on the pour point of different types of lube oils

In this work, we have studied the quantitative composition of seven lube oils obtained from different refineries by Nuclear Magnetic Resonance (NMR) spectroscopy and Gas Chromatography (GC) methods. A trend of low temperature flow behavior of these lube oils has been correlated with the composition, i.e. n-alkane, iso-alkanes and aromatics. The pour point of these lube oils does not depend only on distribution of n-alkanes, rather with quantity and types of other molecules like iso-alkanes and aromatics. Two alkylacrylate co-polymers with different mole fractions of co-monomers synthesized by free radical mechanism are used as pour point depressant (PPD) additives. Effectiveness of additive is dependent on polar aromatic type molecules along with iso-alkane type molecules in lube oil.     

Mass spectra of cyclic ethers formed in the low-temperature oxidation of a series of n-alkanes

Cyclic ethers are important intermediate species formed during the low-temperature oxidation of hydrocarbons. Along with ketones and aldehydes, they could consequently represent a significant part of the heavy oxygenated pollutants observed in the exhaust gas of engines. Apart a few of them such as ethylene oxide and tetrahydrofuran, cyclic ethers have not been much studied and very few of them are available for calibration and identification.Electron impact mass spectra are available for very few of them, making their detection in the exhaust emissions of combustion processes very difficult. The main goal of this study was to complete the existing set of mass spectra for this class of molecules. Thus cyclic ethers have been analyzed in the exhaust gases of a jet-stirred reactor in which the low-temperature oxidation of a series of n-alkanes was taking place. Analyzes were performed by gas chromatography coupled to mass spectrometry and to MS/MS. The second goal of this study was to derive some rules for the fragmentation of cyclic ethers in electron impact mass spectrometry and allow the identification of these species when no mass spectrum is available.     

13C CP/MAS NMR study of accommodation of various organic molecules in (±)-[Co(en)3]Cl3 ionic crystal and their local structure

Accommodation of various organic molecules into a one-dimensional nanochannel of tris(ethylenediamine) cobalt(III) chloride, [Co(en)₃]Cl₃, anhydrated racemic crystal was examined using weight increment measurements, thermogravimetric–differential thermal analysis (TG–DTA), powder X-ray diffraction (PXRD) and ¹³C cross-polarization/magic angle sample spinning (CP/MAS) NMR techniques. Results showed that the (±)-[Co(en)₃]Cl₃ ionic crystal accommodates n-alkanes, n-alkylalcohols, n-alkylamines, and acetonitrile in the 1D nanochannel without decomposition of the crystal lattice. The guest molecules are in all-trans conformation in the nanochannel. Furthermore, the activation energies of uni-axial molecular reorientation of n-alkanes and n-alkylalcohols in the nanochannel were determined using temperature dependence of the ¹H spin–lattice relaxation time in the rotating frame (T_1ρ). Results demonstrated that the activation energy per CH₂ unit (6.5 kJ mol^?1) in n-alkylalcohols was twice that in n-alkanes (3.3 kJ mol^?1), implying the possibility of dimer formation of n-alkylalcohols in the nanochannel by hydrogen bonding through OH group. These findings strongly suggest that the (±)-[Co(en)₃]Cl₃ ionic crystal has adsorption ability to various organic molecules. It will open new avenues to explore new types of zeolites that include ionic crystals.     

Ozone Initiated Oxidation of Hexadecane with Metal Loaded γ-Al2O3 Catalysts

The scope of metal loaded γ-Al₂O₃ materials as catalysts in the ozone initiated functionalisation of higher n-alkanes is investigated at moderate conditions (20 ± 1 °C and ～1 atm). In the ozone initiated oxidation of the higher hydrocarbon, n-hexadecane with 0.5% Pd or Ni or V loaded γ-Al₂O₃ catalysts lead to the keto-isomers as main products, and organic acids as minor products. This paper emphasises the effect of γ-Al₂O₃ catalysts on the conversion, selectivity and reaction products during ozonation of n-hexadecane.     

Fuel properties of hydroprocessed rapeseed oil

This paper deals with the hydroprocessing of rapeseed oil as a source of hydrocarbon-based biodiesel. Rapeseed oil was hydroprocessed in a laboratory flow reactor under four combinations of reaction conditions at temperatures 310 and 360 °C and under hydrogen pressure of 7 and 15 MPa. A commercial hydrotreating Ni-Mo/alumina catalyst was used. Reaction products contained mostly n-heptadecane and n-octadecane accompanied by low concentrations of other n-alkanes and i-alkanes. Reaction product obtained at 360 °C and 7 MPa was blended into mineral diesel fuel in several concentration levels ranging from 5 to 30 wt.%. It was found, that most of the standard parameters were similar to or better than those of pure mineral diesel. On the other hand, low-temperature properties were worse, even after addition of high concentrations of flow improvers.     

Microbial alteration of organic matter of humic coal during biological desulphurisation

The biodegrading influence of biological desulphurisation on bituminous coal and its density fractions was investigated using gas chromatography-mass spectrometry for organic matter alteration and atomic absorption for the assessment of changes in several trace element concentrations. Changes in extract group composition were assessed by comparing the contents of aliphatic, aromatic and polar compounds separated by preparative thin layer chromatography. Aliphatic compounds show extensive alteration due to biodegradation, mainly removal of n-alkanes and lighter acyclic isoprenoids from extracts. The sterane distribution was strongly affected while hopane/moretane distributions show minor changes. Aromatic hydrocarbons were less influenced but some changes were found. It can be assumed that the degree of biodegradation of density fractions increases with increasing concentration of mineral matter since density fractions with lower mineral concentration show smaller changes as a result of biodegradation than those with higher content of minerals. Reduction of concentrations of the following trace elements occurred: beryllium, chromium, zinc, gallium, cadmium, cobalt, lithium, manganese, copper, molybdenum, nickel, lead, and vanadium. The content decrease of an element is not influenced by its geochemical properties. An equally important factor seems to be bonding to organic and inorganic coal substances.     

Thermodynamic and structural analyses of the solid phases in multi-alkane mixtures similar to petroleum cuts at ambient temperature

Structural analyses were carried out by X-ray diffraction, at ambient temperature, on multi-alkane samples whose mole fraction distribution shows a shape of the ‘exponential decreasing’ type, as observed in petroleum cuts. Nine samples, whose normal-alkane number varies from 15 to 23, have been studied with mole fraction continuous distributions of normal-alkanes going from C₂₂-C₃₆ to C₁₄-C₃₆: each mixture differs from the previous sample by the addition of a lighter n-alkane. At the solid state, the multi-alkane solid samples C₂₂-C₃₆ and C₂₁-C₃₆ are two-phase, C₂₀-C₃₆ to C₁₅-C₃₆, three-phase, and the broader distribution C₁₄-C₃₆, four-phase. In these polyphase solid systems, whose heaviest n-alkane is always C₃₆, the average composition of the heavy and middle phases are constant and their structure are isostructural to the β′ ordered intermediate solid solution, observed in n-alkane binary or ternary molecular alloys; the mean carbon atom number of the light phase decreases as the global average carbon atom number of the synthetic mixtures in relation to the addition of light n-alkanes and its structure simultaneously evolves from the β′ ordered intermediate solid solution towards the β-RI(Fmmm) and the disordered solid solutions, observed in pure n-alkanes: the light n-alkane added between each distribution intercalates itself into the structure whose molecule stacking period (thickness) is compatible with its own carbon chain length, in order to reduce the molecular gaps.     

Chemical composition and distribution of the components of valley peat from Amur oblast

The chemical composition of sedge peat from the Egor’evskoe deposit as lowland peat from Amur oblast was characterized. The elemental composition of organic matter and mineral macro- and microcomponents was studied, and the distribution of bitumens, their fractions, and humic acids in the depth of occurrence was revealed. It was found that peat genesis processes occur over the entire vertical profile, and the most converted organic matter is formed at a depth of to 90 cm. The individual composition of alkane fractions consists of C₁₃–C₃₆ normal structure homologues with a carbon preference index somewhat higher than unity; the presence of pristane, phytane, and farnezane was detected. In the fractions of fatty acids, predominantly even compounds from C₁₀ to C₃₀ were identified with special distribution features at the separate stages of peat formation. The analysis of the individual composition of n-alkanes and fatty acids made it possible to supplement botanical characteristics with information on the contribution of macrophytes, algal material, and microorganisms to the formation of the organic matter of peat.