Experimental solubility data of various n-alkane waxes: effects of alkane chain length,alkane odd versus even carbon number structures,and solvent chemistry on solubility

Solubility data were measured for eight different n-alkanes ranging from tetracosane to tetratetracontane (C₂₄H₅₀–C₄₄H₉₀). Included are: (1) solubility data in toluene for all the n-alkanes studied and (2) solubility data of n-hexatriacontane (C₃₆H₇₄) in several solvent and solvent mixture systems. Illustrated in the data are the effects on solubility of alkane chain length, alkane odd versus even carbon number structures, and solvent chemistry. The measurements were made to provide fundamental equilibrium data.     

Application of hollow fiber liquid-phase microextraction in identification of oil spill sources

In this study, hollow fiber based liquid-phase microextraction (HF-LPME), coupled with GC, GC–MS and GC–IRMS detections, was employed to determine petroleum hydrocarbons in spilled oils. According to the results, the HF-LPME method collected more low-molecular weight components, such as C₇–C₁₁n-alkanes, naphthalene, and phenanthrene, than those collected in conventional liquid–liquid extraction (LLE). The results also showed that this method had no remarkable effect on the distributions of high-molecular weight compounds such as >C₁₈n-alkanes, C₁–C₃ phenanthrene, and hopanes. Also, the carbon isotopic compositions of individual n-alkanes in the two preparation processes were identical. Accordingly, HF-LPME, as a simple, fast, and inexpensive sample preparation technique, could become a promising method for the identification of oil spill sources.     

(Liquid + liquid) equilibria of binary systems containing hyperbranched polymer Boltorn® H2004 – Experimental study and modelling in terms of lattice-cluster theory

(Liquid + liquid) phase equilibria (LLE) of binary mixtures containing hyperbranched polymer Boltorn® H2004 and n-alkanes (n-hexane, n-heptane, n-octane, and n-decane) were studied over the temperature range from about (260 up to 360) K. The polymer is partially miscible with n-alkanes and the solubility decreases with an increase of the chain length of the solvent. Corresponding LLE phase diagrams including spinodal and binodal (liquid + liquid) coexistence curves were calculated in terms of the statistical mechanics – based on the lattice-cluster theory, based only on the upper critical solution temperature, and the polymer chain architecture. The results show semi-qualitative agreement of predicted and experimental equilibrium compositions and temperatures. Boltorn® H2004 reveals complete miscibility in the liquid phase with alcohols (C₁–C₈), aromatic hydrocarbons (benzene, toluene, and thiophene), and ethers (methyl tetra-butyl ether, ethyl tetra-butyl ether, and tetrahydrofurane).     

Heat Capacity Estimation Using a Complete Set of Homodesmotic Reactions for Organic Compounds

Reliable information about isobaric heat capacities C_P is necessary to determine the energies of organic compounds and chemical processes at an arbitrary temperature. In this work, the possibility of theoretical estimation of C_P by the homodesmotic method is analyzed. Three cases of C_P calculation applying the methodology of the complete set of homodesmotic reactions (CS HDRs) are considered: the gas- and liquid-phase C_P of organic compounds of various classes at 298 K (the mean absolute value of reaction heat capacity, MA ΔC_P = 1.44 and 2.83 J/mol·K for the gas and liquid phase, correspondingly); and the gas-phase C_P of n-alkanes C₂–C₁₀ in the temperature range of 200–1500 K with an average error in calculating the heat capacity of 0.93 J/mol·K. In the latter case, the coefficients of the Shomate equation are determined for all n-alkanes that satisfy the homodesmoticity condition. New values of gas- and liquid-phase heat capacities are obtained for 41 compounds. The CS HDRs-based approach for estimating the C_P of organic compounds is characterized by high accuracy, which is not inferior to that of the best C_P-additive schemes and allows us to analyze the reproducibility of the calculation results and eliminate unreliable reference data.     

Identification of endogenous and anthropogenic hydrocarbons in bottom deposits of peat lakes and evaluation of their contribution to the “hydrocarbon index”

Gas chromatography with mass spectrometric detection was used to analyze bitumens isolated from bottom sediments of peat lakes contaminated with petroleum products. Endogenous hydrocarbons are characterized by the presence of n-alkanes with an odd number of carbon atoms in the molecule in the characteristic region of C₂₃–C₃₃, the absence of a “hump” characteristic of oil products in the chromatogram, and the presence of light hydrocarbons, eluting in the initial part of the chromatogram (light hydrocarbons are usually lost when the sample is dried). The distribution profile of odd n-alkanes is used to assess the contribution of endogenous hydrocarbons to the “hydrocarbon index” with the help of the pattern recognition method. The concentration of light hydrocarbons is from 50 and 300–400 to 3500–5000 mg/kg for a number of samples and even up to 26000 mg/kg in some samples. The concentration of petroleum hydrocarbons and heteroatomic compounds varies from the lowest values of 30–80 mg/kg up to 20000 mg/kg and higher.     

The adsorption properties of titanium dioxide

The adsorption properties of titanium dioxide were studied by gas chromatography. We used organic compounds from different classes, namely, n-alkanes, n-alkenes (C₆-C₈), and polar compounds (electron donors and acceptors) as test adsorbates. The differential heats of adsorption and the contributions of dispersion and specific intermolecular interaction energies were determined for the systems from the experimental retention data. The electron-donor and electron-acceptor characteristics of the ultimately hydroxylated surface of TiO₂ were evaluated.     

Chromatographic properties of fullerene modified with liquid crystal p, p′-azoxyphenetol

Stationary phases for gas chromatography based on liquid crystal p,p′-azoxyphenetol applied onto Chromaton N-AW bearing a layer of C₆₀ fullerene were studied. The thermodynamic properties of the adsorption of n-alkanes and n-alcohols on the mesogen surface were studied at low occupancies. Test mixtures of structural isomers of substituted benzene and polycyclic aromatic hydrocarbons were analyzed in a wide temperature range from 100 to 240°C.     

Generation,sampling and chromatographic analysis of particulate matter in dilute sidestream tobacco smoke

The sampling and gas chromatographic separation of the particulate matter of sidestream tobacco smoke for high-molecular-weight compounds are described. Four n-alkanes (C₂₇, C₂₉, C₃₁ and C₃₃) were identified and their relationship to the particulate levels was established. The sidestream yields of these compounds for several cigarette types, including regular, low- and ultra-low-tar filtered and high-tar unfiltered varieties are reported. Concentrations in diluted smoke at particulate levels similar to ambient tobacco smoke were also determined. Methods for generating test atmospheres of sidestream smoke at low-level, uniform concentrations are described.     

Separation of alkanes and aromatic compounds by packed column gas chromatography using functionalized Multi-Walled Carbon Nanotubes as stationary phases

In the present work, we show a novel application of pristine and functionalized Multi-Walled Carbon Nanotubes (MWCNTs) as stationary phase in low-cost packed columns for the gas chromatographic separation of alkanes and aromatic hydrocarbons. The MWCNTs were deeply investigated by means of physical and chemical methods, like thermal analysis, IR and atomic force microscopy, and Inverse Gas Chromatography (IGC) in order to correlate the adsorption process and surface properties with the material purity level and functionalization degree. The derivatization process of the pristine nanotubes was a key factor to achieve a successful separation of both the light n-alkanes (C₃–C₅) and the related isomers (C₄–C₅ branched alkanes). Satisfactory results were similarly obtained in the case of separation of aromatic hydrocarbons (BTX).     

Viscosity of heavy n-alkanes and diffusion of gases therein based on molecular dynamics simulations and empirical correlations

The viscosity of pure n-alkanes and n-alkane mixtures was studied by molecular dynamics (MD) simulations using the Green–Kubo method. n-Alkane molecules were modeled based on the Transferable Potential for Phase Equilibria (TraPPE) united atom force field. MD simulations at constant number of molecules or particles, volume and temperature (NVT) were performed for n-C₈ up to n-C₉₆ at different temperatures as well as for binary and six-component n-alkane mixtures which are considered as prototypes for the hydrocarbon wax produced during the Gas-To-Liquid (GTL) Fischer–Tropsch process. For the pure n-alkanes, good agreement between our simulated viscosities and existing experimental data was observed. In the case of the n-alkane mixtures, the composition dependence of viscosity was examined. The simulated viscosity results were compared with literature empirical correlations. Moreover, a new macroscopic empirical correlation for the calculation of self-diffusion coefficients of hydrogen, carbon monoxide, and water in n-alkanes and mixtures of n-alkanes was developed by combining viscosity and self-diffusion coefficient values in n-alkanes. The correlation was compared with the simulation data and an average absolute deviation (AAD) of 11.3% for pure n-alkanes and 14.3% for n-alkane mixtures was obtained.     

Prediction of molecular weight and density of n-alkanes (C6-C44)

Heavy n-alkanes and their mixtures were characterized by high temperature-simulated distillation using gas chromatography with a capillary column. In this work, the atmospheric boiling point is determined by the HT-SimDis GC method. In this study, molecular weights and density of n-alkanes were evaluated with this method by using retention times and normal boiling points as input data. ASTM D2887 calibration mixture containing 17 n-alkanes in the C₆-C₄₄ range were used for qualitative analyses. Retention times (t_R) of n-alkanes were measured with this method. The other input data that normal boiling points (T_b) and molecular weight (M) had been taken in the literature. Experimental densities (at 20 °C) of n-alkanes were obtained from API Research Projects. Empirical molecular weight and density correlations were developed by using the nonlinear and multiple regressions with correlation coefficients. The results of calculations were compared with experimental data. Normal boiling point predictions were obtained as an average absolute deviation of 1.07%. Molecular weight and density results were evaluated as average absolute deviations of 0.68% and 0.21%, respectively.     

Chromatographic study of the organic matter from Moroccan Rif bituminous rocks

The bituminous rocks of the Upper Cretaceous in the Moroccan Rif have been assessed and characterized in detail using organic geochemical techniques and a variety of organic geochemical parameters. The organic matter from 4 sites was studied in order to determine its thermal maturity and its depositional environments. The organic extracts (bitumens) were fractionated on silica-potassium hydroxide column according to the aliphatic hydrocarbons, acid compounds and polar compounds. Aliphatic hydrocarbons were identified by gas chromatography and mass spectrometry (GC/MS).The distribution of the aliphatic hydrocarbon fractions, and the various organic geochemical parameters (pristane/phytane, isoprenoids/n-alkanes, CPI, C₂₇:C₂₈:C₂₉ regular, C₂₉20S/(20S+20R), C₂₉ββ/(ββ+αα), C₂₉/C₃₀ hopanes and Ts/Tm) showed that the studied samples were generally mature. Two of the 4 samples appeared to be derived from source rocks deposited under anoxic conditions while suboxic to oxic conditions seemed to have been dominant for the remaining two samples. Rock–Eval pyrolysis data in addition to GC results suggested types II, III and IV kerogens for the studied samples.     

Phase equilibria for binary n-alkanenitrile—n-alkane mixtures. I. Upper liquid—liquid coexistence temperatures for ethanenitrile,propanenitrile, and n-butanenitrile with some C5C18n-alkanes

The upper critical solution temperatures (UCST's) of 26 n-alkanenitrile—n-alkane mixtures containing CH₃CN, C₂H₅CN, and C₃H₇CN with C₅C₁₈n-alkanes have been estimated experimentally. The UCST's diminish with increasing nitrile chain length and increase with increasing alkene chain length. The results are described well by the Weimer—Prausnitz modification of the regular solution theory incorporating a Flory—Huggins entropy of mixing.     

Application of urea adduction technique to polluted urban aerosols for the determination of hydrogen isotopic composition of n-alkanes

We examined an applicability of an improved urea adduction technique for the determination of hydrogen isotopic composition (δD) of homologous series of n-alkanes present in polluted urban aerosols using GC/TC/IRMS. Unresolved complex mixture (UCM) of hydrocarbons that interferes with accurate isotope measurements of n-alkanes was removed from n-alkane fraction by a urea adduction method. Recoveries of C₂₀ to C₃₀ n-alkanes during the urea adduction procedure were greater than 90% when the concentrations of total n-alkanes exceed 6.1?µg?mL^?1. Our compound-specific D/H ratios confirm the absence of significant hydrogen isotope fractionation in n-alkanes during urea adduction and recovery of the purified n-alkane fraction. We applied this technique to the urban aerosols that contain a large quantity of UCM to measure δD of C₂₀ to C₃₅ n-alkanes in urban aerosols from Tokyo and Sapporo with an accuracy less than 10‰. We found that the δD values widely ranged from ?38 to ?179‰. Based on the δD values of individual n-alkanes in aerosol samples, we can obtain further information on the sources of aerosol n-alkanes and their source regions, and the atmospheric processes such as long-range transport and atmospheric mixing of air masses of different origin.     

Diffusion of linear paraffins in silicalite studied by the ZLC method in the presence of CO2

The diffusion behavior of C₄–C₁₀ n-alkanes in silicalite-1 has been investigated by using the Zero Length Column method. The diffusivities derived from measurements at different purge rates with different purge gases confirming intracrystalline diffusion control. Data are compared with results reported in the literature for MFI zeolites. The diffusivities were found to be consistent and agree well with data previous obtained by ZLC. However, these data showed a remarkable disagreement with other reported techniques (PFG-NMR, QENS and Permeation). The eventual influence of carbon dioxide (CO₂) adsorption on diffusion properties of n-alkanes in silicalite was also investigated. For this purpose, a series of experiments was performed involving hydrocarbons mixed with CO₂. Data were obtained at 303 K and flow rates between 20 and 80 mL/min. The presence of CO₂ does not seem to influence the intracrystalline transport rate of the investigated light hydrocarbons (n-C₄ and n-C₆). On the other hand, the situation for n-C₈ and n-C₁₀ is more complex. The diffusivity values are higher compared to the previously reported values.     

Study of the Hyflon AD80 perfluorinated copolymer by inverse gas chromatography

The perfluorinated copolymer of tetrafluoroethylene and perfluoromethoxydioxole, Hyflon® AD80x, is investigated by inverse gas chromatography. C₅–C₁₃ n-alkanes are used as sorbates, for which the specific retention volume, the solubility coefficient at infinite dilution, and the excess thermodynamic functions are calculated in the temperature range 30–115°C. The solubility coefficients of the hydrocarbons in the studied polymer are shown to be lower than those in amorphous Teflons AF1600 and AF2400, a finding that is consistent with the difference between the glass-transition temperatures of these polymers. The correlation between excess partial molar enthalpies and critical volumes of n-alkanes testifies that the upper limit for the size of the free-volume element in this polymer is 613 ų. Mixing of n-alkanes with Hyflon AD80 is thermodynamically disadvantageous (\(\bar G_1^{E,\infty } \) > 0) and becomes even less advantageous with an increase in the size of hydrocarbon molecules. Excess entropy mainly contributes to the high values of excess free energy, thus indicating a higher order in the system containing the glassy polymer than that in systems in which the polymer occurs in the rubberlike state.     

Selective Separation of Oxy-PAH from n-Alkanes and PAH in Complex Organic Mixtures Extracted from Airborne PM2.5

A fast and simple fractionation method was optimized to selectively separate oxy-PAH from polycyclic aromatic hydrocarbons (PAH) and n-alkanes contained in solvent extracted organic matter (SEOM) from atmospheric particles with an aerodynamic diameter ≤2.5 μm (PM_2.5). Samples were collected in Mexico City. Multivariate parameters were adjusted on a standard mixture, and on SEOM spiked with pure standard mixture solutions: type and amount of phase; packing densities; type, proportion and amount of solvents, and elution flow rates were tested under several elution schemes. Cyanopropylsilyl-bonded phase material was the selected stationary phase. The separation method was applied to real samples of SEOM (2.6, 5.6 and 8.5 mg) spiked with n-alkanes, PAH and oxy-PAH. n-Alkanes overlapped with PAH due to an excess of n-alkanes in real samples overloading the capacity of the stationary phase. Oxy-PAH was separated totally from n-alkanes and PAH. Mean recoveries ± confidence intervals (95%) for n-alkanes ranged from 53 ± 17% (n-tetracontane) to 101 ± 11% (n-hexacosane); for PAH from 58 ± 5% (phenanthrene) to 85 ± 9% (benzo[k]fluoranthene); and for oxy-PAH from 68 ± 12% (9,10-dihydrobenzo[a]pyren-7(8H)one) to 108 ± 9% (1,2-benzopyrone). This method is an efficient fractionation procedure to be applied to oxy-PAH, PAH and n-alkanes in complex organic mixtures extracted from PM_2.5.     

The thermodynamic parameters of sorption and enantioselectivity of the chiral smectic liquid crystal 2-methylbutyl ester of 4-(4-decyloxybenzylideneamino)-cinnamic acid

The thermodynamic characteristics of sorption of n-alkanes, arenes, aldehydes, monoatomic alcohols, and optical isomers of camphene and butanediol-2,3 by a chiral smectic liquid crystal, 2-methylbutyl ester of 4-(4-decyloxybenzylideneamino)-cinnamic acid, from the gas phase were studied over the temperature range including the S*_C and S*_A mesophases and isotropic phase. The standard and excess thermodynamic functions of sorption were determined for 26 sorbates of the classes of substances specified. The S*_C and S*_A mesophases exhibited selectivity with respect to the separation of para and meta xylenes (α _p/m = 1.06–1.07, 90–108°C) and pronounced enantioselectivity (α_R/S = 1.05–1.09, 87–108°C). The helically twisted structure of the smectic liquid crystal was shown to play an important role in the mechanism of the chiral recognition of optical isomers of polar and low-polarity compounds under gas-liquid chromatography conditions.     

Thermophysical properties and thermodynamic phase behavior of ionic liquids

The thermal stability of many tested ionic liquids (ILs) was investigated by the TGA and DTA curves over the wide temperature range from 200 to 780 K. The TGA curves have mainly a sigmoid shape, which can be split into three segments. The thermal decomposition of the samples was higher than 500 K. For the ammonium salts, C₂BF₄, or C₂PF₆, or C₂N(CN)₂, or C₄Br, the temperatures of the decompositions were 583.5, 556.1, 545.1 and 525.3 K, respectively. Generally, it was found that the temperature of decomposition of investigated ionic liquid is strongly depended on the type of cation and the anion. Phase equilibria and thermophysical constants were measured also for the dialkoxy-imidazolium ILs, [(C₄H₉OCH₂)₂IM][BF₄], [(C₈H₁₇OCH₂)₂IM][Tf₂N], [(C₁₀H₂₁OCH₂)₂IM][Tf₂N] and for pyridinium IL, [Pyr][BF₄].The characterization and purity of the compounds were obtained by the elemental analysis, water content (Fisher method) and differential scanning microcalorimetry (DSC) analysis. From (DSC) method, the melting points, the enthalpies of fusion, the temperatures and enthalpies of solid-solid phase transitions and the half C_p temperatures of glass transition of all investigated ionic liquids were measured.The phase equilibria of these salts with common popular solvents: water, or alcohols or n-alkanes, or aromatic hydrocarbons have been measured by a dynamic method from 290 K to the melting point of IL, or to the boiling point of the solvent in the whole mole fraction range, x from 0 to 1.These salts mainly exhibit simple eutectic systems with immiscibility in the liquid phase with upper critical solution temperatures (UCST), not only with aromatic hydrocarbons, cycloalkanes and n-alkanes but also with longer chain alcohols. For example the C₂BF₄ salt show simple eutectic system with water and simple eutectic systems with immiscibility in the liquid phase with upper critical solution temperature with alcohols.The solid-liquid phase equilibria, SLE curves were correlated by means of the different G^Ex models utilizing parameters derived from the SLE. The root-mean-square deviations of the solubility temperatures for all calculated data depend on the particular system and the equation used.     

Prediction of activity coefficients and Henry's constants at infinite dilution for mixtures of n-alkanes

Trejo Rodríguez, A. and Patterson, D., 1984. Prediction of activity coefficients and Henry's constants at infinite dilution for mixtures of n-alkanes. Fluid Phase Equilibria, 17: 265–279.The corresponding-states principle (CSP) for chain molecules has been used to predict activity coefficients γ_i^∞ at infinite dilution and Henry's constants H_i,j for mixtures of n-alkanes. The mixtures for which predictions of γ_i^∞ are made include n-C₄ through n-C₁₀ as the solute in several pure higher n-alkanes, at several temperatures from 30 to 90°C. Predictions of H_i,j are made for mixtures where the solute is C₂ through n-C₈ and the solvent any n-alkane from n-C₄ through n-C₂₂, also at several temperatures, from –15 to 177°C. The predicted values are compared with experimental data from the literature, and in all cases the agreement is remarkably good. The temperature dependence of H_i,j for some mixtures is used to derive heats of solution ΔH_s, and comparison is again carried out with available experimental values.