Polar compounds, petroleum

Extraction Solvent. Dimethyl sulfoxide is immiscible with alkanes but is a good solvent for most unsaturated and polar compounds. Thus, it can be used to separate olefins from paraffins (93). It is used in the Institute Fransais du Pntrole (IFF) process for extracting aromatic hydrocarbons from refinery streams (94). It is also used in the analytical procedure for determining polynuclear hydrocarbons in food additives (qv) of petroleum origin (95). 

Molecular sieves (dehydrated zeolite) purify petroleum products with their strong affinity for polar compounds such as water, carbon dioxide, hydrogen sulfide, and mercaptans. The petroleum product is passed through the sieve until the impurity is sufficiently removed after which the sieve may be regenerated by heating to 400 - bOO F. 

Coupled LC-LC can separate high-boiling petroleum residues into groups of saturates, olefins, aromatics and polar compounds. However, the lack of a suitable mass-sensitive, universal detector in LC makes quantitation difficult SFC-SFC is more suitable for this purpose. Applications of multidimensional HPLC in food analysis are dominated by off-line techniques. MDHPLC has been exploited in trace component analysis (e.g. vitamin assays), in which an adequate separation for quantitation cannot be achieved on a single column [972]. LC-LC-GC-FID was used for the selective isolation of some key components among the irradiation-induced olefinic degradation products in food, e.g. dienes and trienes [946],... 

The techniques employed to extract the analytes of interest can frequently extract interfering compounds. Polar compounds such as animal and plant fats, proteins, and small biological molecules may be identified incorrectly as petroleum constituents. Extract cleanup techniques can be used to remove them. In an ideal situation, only interfering compounds are removed. In reality, some polar petroleum constituents can also be removed. 

Eor the analysis of petroleum hydrocarbons, a moderately polar material stationary phase works well. The plate is placed in a sealed chamber with a solvent (mobile phase). The solvent travels up the plate, carrying compounds present in the sample. The distance a compound travels is a function of the affinity of the compound to the stationary phase relative to the mobile phase. Compounds with chemical structure and polarity similar to those of the solvent travel well in the mobile phase. For example, the saturated hydrocarbons seen in diesel fuel travel readily up a plate in a hexane mobile phase. Polar compounds such as ketones or alcohols travel a smaller distance in hexane than do saturated hydrocarbons. 

The application of biomarker research in the geologic record has dealt with the derivative hydrocarbons as found in petroleum, coals, and sedimentary rocks. Reports on biomarkers in discrete fossils compared to the host rocks are sparse because (1) previous studies focused on the highly degraded geoterpenoids, i.e. saturated and aromatic hydrocarbons, and (2) the preservation potential of polar compounds (natural product bioterpenoids ) was believed to be low. Flowever, recent investigations of conifer fossils demonstrated that unaltered natural product terpenoids can be preserved in resin material.This will be illustrated here with an example. 

Dry milled plant material was thoroughly extracted with petroleum ether/ether (2 1) (67). The extracts were separated on a kieselgel 60 silica column, and eluted with petroleum ether/ethyl acetate and ethyl acetate/methanol mixtures of increasing polarity. Compounds were further purified by silica TLC using a variety of solvents or on a HPLC, Dynamax semipreparative silica column, with 98% hexane/2% dichloromethane solvent. 

After separation of neroli oil, the aqueous layer of the steam distillate, known as orange blossom water, is extracted with suitable solvents (e.g., petroleum ether). Evaporation gives orange flower water absolute (absolue de Teau de fleurs d oranger), which is a dark brown-red liquid. It contains less terpene hydrocarbons and correspondingly more polar compounds than neroli oil. 

The solubility of molecules can be explained on the basis of the polarity of molecules. Polar, e.g. water, and nonpolar, e.g. benzene, solvents do not mix. In general, like dissolves like i.e., materials with similar polarity are soluble in each other. A polar solvent, e.g. water, has partial charges that can interact with the partial charges on a polar compound, e.g. sodium chloride (NaCl). As nonpolar compounds have no net charge, polar solvents are not attracted to them. Alkanes are nonpolar molecules, and are insoluble in polar solvent, e.g. water, and soluble in nonpolar solvent, e.g. petroleum ether. The hydrogen bonding and other nonbonding interactions between molecules are described in Chapter 2. 

Nonaqueous Liquid Wastes Protocol. Nonaqueous liquid wastes were defined to include samples that range from water-soluble organic liquids to immiscible oils. Only a limited amount of data are available on the applicability of this protocol (Figure 4) to compounds other than oils or petroleum products. This medium differs from other environmental media because mutagenic materials are often concentrated in organic liquids. Therefore, this protocol incorporates dilution steps rather than the concentration techniques used in the other media protocols. This protocol is also unique because of the opportunity to test neat samples or samples diluted with DMSO rather than sample components isolated with an absorbent or extracted with a solvent. For this reason, samples treated with this protocol should contain polar compounds and/or volatile compounds that would be lost when the other protocols are used. 

Sauer and Fitzgerald [9] have described thin layer chromatographic technique for the identification of water-borne petroleum oils. Aromatic and polar compounds are removed from the sample by liquid-liquid extraction with acidified methanol, the extract is chromatographed on a silica gel thin layer plate, and the separated components are detected by their fluorescence under long- and short-wave ultraviolet light. Unsaturated non-fluorescing compounds are detected by iodine staining. 

Galimberti R., Ghiselli C., and Chiaramonte M. A. (2000) Acidic polar compounds in petroleum a new analytical methodology and applications as molecular migration indices. Org. Geochem. 31, 1375-1386. 

Detailed analysis of residual products, such as residual fuel oil, is more complex than the analysis of lower-molecular-weight liquid products. As with other products, there are a variety of physical property measurements that are required to determine whether the residual fuel oil meets specification, but the range of molecular types present in petroleum products increases significantly with an increase in the molecular weight (i.e., an increase in the number of carbon atoms per molecule). Therefore, characterization measurements or studies cannot, and do not, focus on the identification of specific molecular structures. The focus tends to be on molecular classes (paraffins, naphthenes, aromatics, polycyclic compounds, and polar compounds). 

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