Aromatic Hydrocarbons
An aromatic hydrocarbon contains one or more planar sets of six carbon atoms. The simplest aromatic hydrocarbon is benzene and the set of six carbon atoms is called the benzene ring. The benzene ring is usually drawn with alternating double bonds. There is a reason for this. Each carbon atom has four electrons to share, one shares with the hydrogen atom, and one each to the two neighboring carbons leaving one extra to share with one of its neighboring carbon atoms (i.e. a double bond). Aromatic bonding is a type of bonding quite distinct from other types of multiple bonding, such as double or triple bonds. Two fused benzene rings produce the hydrocarbon naphthalene and three fused benzene rings produce the two isomers anthracene and phenanthrene. The hydrogen atoms on benzene, for example, can be substituted by a methyl group or ethyl group producing methyl benzene (toluene) or ethyl benzene. Aromatic hydrocarbons are present in relatively large quantities in coal-gas extracts. The gas is washed with oil and the ‘benzole’ distilled from the oil producing a ‘benzole mixture’. The benzole mixture contains about 70%v/v of benzene, about 20%v/v of toluene, about 5%v/v of the higher aromatics and about 5%v/v of aliphatic hydrocarbons, naphthenes and olefins (typical ofcoke oven benzole). The carbon/hydrogen ratio of the aromatics is high so their presence in coal gas give the gas its luminosity when burnt. Unlike aliphatic compounds which undergo nucleophilic substitution reactions, aromatic hydrocarbons undergo electrophylic substitution reactions.
Author: RPW Scott
Book:Gas Chromatography - Tandem Techniques
Section:GC-Tandem Modern-Systems Light-Pipe-Interfaces
sensitivity could be achieved for each aromatic or group of aromatic hydrocarbons. Diehl et al. used a Hewlett-Packard Model 5890 Series II GC/5965 IRD FTIR, with an open tubular column 60 m long and 0.53 mm I.D., carrying a 5.0 mm film of stationary phase on the internal surface. The column was programmed from 40ûC to 190 ûC at 2ûC per min. and then to 300ûC at 30ûC per min. The light pipe and the transfer line were held at 300ûC. By using appropriate wavelengths, the elution of the aromatic hydrocarbons could be exclusively monitored. The chromatograms obtained are shown in figure 41. The separation was fairly lengthy, extending well over an hour but this investment in time was repaid in selectivity. The aromatic hydrocarbons are exclusively monitored, and the numerous aliphatic and unsaturated hydrocarbons, (also present in the mixture) gave little or no response at the selected wavelength
GC-Tandem Modern-Systems Light-Pipe-Interfaces
Author: RPW Scott
Book:The Mechanism of Chromatographic Retention
Section:Retention Chromatographic-Interactions Polar Dipole-Induced-Dipole
compounds are the
aromatic hydrocarbons. However, just as dipole-dipole interactions occur
coincidentally with dispersive interactions, so are dipole-induced dipole
interactions accompanied by dispersive interactions. It follows that using an n-alkane
stationary phase, aromatic hydrocarbons can be retained and separated by purely
dispersive interactions as in GC. This again is demonstrated in the upper
chromatogram in figure 1. Alternatively, a polyethylene glycol stationary phase
will separate aromatic hydrocarbons largely by dipole-induced dipole
interactions combined with some dispersive interactions. This effect is
also demonstrated in the lower chromatogram in figure 2.
Molecules can
exhibit multiple interactive properties. For example, phenyl ethanol possesses
both a dipole as a result of the hydroxyl group and is polarizable due to the
aromatic ring. Phenyl acetic acid contain groups that will provide dispersive
interactions(the methylene group and the aromatic ring),
Retention Chromatographic-Interactions Polar Dipole-Induced-Dipole
Author: RPW Scott
Book:Principles and Practice of Chromatography
Section:Principles Applications Gas-Chromatography Hydrocarbon-Analysis
phase Supelcowax
10. This stationary phase is strongly polar and corresponds to a bonded
polyethylene glycol. The strong fields from the hydroxyl groups polarize the
aromatic nuclei of the aromatic hydrocarbons and thus retention was effected
largely by polar interactions between the permanent and induced dipoles of the
stationary phase and solute molecules respectively.
Courtesy of Supelco Inc.
Figure 38
The Separation of 10 ppb Quantities of Aromatic Hydrocarbons from Water
The flow rate
was 10 ml/min. in conjunction with the FID detector. The column was held at
50˚C for 8 min. and then programmed to 100˚C at 4˚C per min.
More than adequate separation is achieved and even the m and p xylenes
are well resolved. This might indicate that a significantly shorter analysis
was possible. The aromatic hydrocarbons were present in the original aqueous
solution at 10 ppb and so the 5 ml of water contained about 50 pg
Principles Applications Gas-Chromatography Hydrocarbon-Analysis
Author: RPW Scott
Book:Principles and Practice of Chromatography
Section:Principles Applications Gas-Chromatography Hydrocarbon-Analysis
Hydrocarbon Analysis
Due to the perceived toxicity and
carcinogenic character of the aromatic hydrocarbons, the presence of
these materials is carefully monitored in all areas where they might
enter the human food chain. The analysis of water for aromatic
hydrocarbons, particularly surface water in those areas where
contamination might take place, is a common assay made by the public
analyst. It is essential to be able to measure concentrations in the
ppb levels, and thus GC method employing a high sensitive detector
is essential. Nevertheless, even if a high sensitivity detector is
employed, some sample concentration will be necessary to measure
contaminants at such low levels. One method is the purge and trap
Principles Applications Gas-Chromatography Hydrocarbon-Analysis
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Emissivity-or-Photometric-Detector
areas of application. It was originally used to differentiate aromatic
from paraffinic hydrocarbons by measuring the luminosity that the aromatic
nucleus imparted to the flame. Contemporary photometric detectors do not
usually monitor the total light emitted only light emitted at specific
wavelengths. For example, phosphorus and sulfur containing hydrocarbons
generate chemi-luminescence at specific wavelengths when burnt in the hydrogen
flame. The wavelengths of the light emitted by carbon and hydrocarbons
containing sulfur and phosphorus are shown in figure 25.
Courtesy of the Hewlett–Packard Corporation
Figure
25 Light Emission Wavelengths of Carbon and Hydrocarbons Containing Sulfur and Phosphorus
GC-Detectors Emissivity-or-Photometric-Detector
Author: RPW Scott
Book:Principles and Practice of Chromatography
Section:Principles Selectivity Polar
An example of
the use of induced dipoles to separate polarizable substances is afforded by
the analysis of some aromatic and nitroaromatic hydrocarbons by LC using silica
gel as the stationary phase.
Courtesy of Supelco Inc.
Figure 14 The Separation
Aromatic and Nitro-Aromatic Hydrocarbons
A small-bore
column 25 cm long and 1 mm I.D. was employed, packed with silica gel having a
particle diameter of 10 m. The mobile
phase was n-hexane at a flow-rate 50 ml
per min. The solutes of interest are naphthalene and pyrene, the first two
peaks. The two solutes are well separated
Principles Selectivity Polar