EXPERIMENT 4 ANALYSIS OF HYDROCARBONS IN COMMON FUELS BY SOLID-PHASE MICROEXTRACTION (SPME) AND GAS CHROMATOGRAPHY MASS SPECTROMETRY

Introduction Gasoline, diesel and kerosene are all created from crude oil by a variety of refining and distillation processes. Each product is produced by the combination of multiple individual hydrocarbon compounds all of which have slightly different vaporization and boiling temperatures. Gasoline is the combination of many lower boiling range compounds while the middle boiling range compounds are used in differing proportions to create kerosene and diesel. The profile of hydrocarbons in oil may hence be used to characterize the oil. This enables the identification of the candidate source of oil spill cases.

Solid-phase microextraction (SPME) parameters were examined on water contaminated with hydrocarbons including benzene and alkylbenzenes, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs). Sample preparation is an essential step in analysis, greatly influencing the reliability and accuracy of analysis. It is a rapid, inexpensive and solventless technique for the isolation of organic compounds from gaseous and liquid sample. It is based on the enrichment of the analytes on a polymer or adsorbent coated fused silica fiber by exposing the fiber directly or to do its headspace and thermal desorption of the analytes in the GC injector. In this experiment, the components of hydrocarbons in common fuels are identified using SPME-GC-MS

SPME Apparatus The SPME apparatus consist of a fiber holder and a fiber assembly, the latter containing a 1 to 2 cm long retractable SPME fiber. The SPME fiber is a thin fused-silica optical fiber (polydimethylsiloxane, PDMS) Factor that effect SPME performance Coating material The most important features determining the analytical performance of SPME is the type and thickness of the coating material. The selectivity of extraction depends on the type of fiber. In general, polar fibers are used for polar analytes and non-polar fibers for non-polar analytes as with the conventional GC stationary phases. The use of a thicker fiber requires a longer extraction time but the recoveries are generally higher. The time of extraction is independent of the concentration of analyte in the sample and the relative number of molecules extracted at a distinct time is also independent of the concentration of analyte. Usually the thinnest acceptable film is employed to reduce extraction times. Extraction Procedure The coated fibre is immersed directly in the sample or the headspace of the sample, where the analytes are concentrated. After equilibrium has been reached (froma few minutes to several hours depending on the properties of the analytes measured) or after a defined time the fiber is withdrawn and transferred either to a GC injection port. The extraction efficiency and the time required to reach equilibrium can be influenced by several factors that include extraction temperature, sample agitation, volatility of analytes and type, thickness of fiber coating.

Sample Accelerates: Unleaded petrol, diesel, paint thinner and kerosene.

Apparatus: SPME holder with 100 m polydimethylsiloxane (PDMS) fibre. Instrument 1. Gas chromatograph (Agilent Technologies 5890 Series II) equipped with HP 5971A mass selective detector and a 30 m x 250 m x 0.25 m HP 5-MS capillary column. 2. Glass vial with septum.

Analytical Procedure 1. Instrument set-up Injector temperature Detector temperature Carrier gas flow rate Column temperature : 250 C : 300 C : 30 mL/s : 60 C to 170 C/min

2. SPME Procedure i. The fiber condition in the GC injection port at 250 C for at least 10 minutes to removes contaminants. ii. 5 mL of sample was adding approximately in a glass vial and the vial was place on a hot plate. The sample was heat up to 50 C. The sample was agitated by using the magnetic stirrer. iii. iv. v. The SPME fiber was exposed to the headspace of the vial for 20 minutes Withdraw the fiber into the needle, pull out from the vial and immediately inject into the GC-MS with a desorption time 80 second. Using the mass spectra library, identify the major compounds in each sample using the mass spectra library.

Discussion: In this experiment, the sample preparation used solid phase microextraction (SPME).SPME reduces the time necessary for sample preparation, decreases purchases and disposal costs of solvents and can improve detection limits. That is why the SPME was choose in this analysis. From this experiment, there are four chromatograms obtain which are kerosene, petrol, diesel and unknown. The method used was SPME where it used fiber to absorb the sample. Needle with fiber was put into the sample by head space method. The sample was volatile and thermally stable. So it does not need to dip it into the sample. The sample was volatile when it heated and the fiber absorbs the sample volatile and keeps it in the fiber. The first chromatogram obtain was diesel sample. There are eight main components in the sample. However only four components with the high quality were taken and the structure were taken from the library of the mass spectrometer. The components taken were heptadecane with 97 quality, hexadecane with 98 quality, tetradecane with 97 quality, and p-xylene with 95 qualities. The second sample was injected was kerosene. There were a lot of component in this sample which were 31 component found in the chromatogram. The biggest quality for the component to read in the library were undecane with 94 quality, benzene, 1-methyl-3-prophyl with 90 quality, decane with the 94 quality, and tetradecane with a quality of 98. The third sample injected was petrol there are nine component found in this sample. Unfortunately only three components were taken to detect the structure. First structure with the 95 quality was benzene, 1, 2, 3,-trimethyl. Second component was p-xylene with 95 qualities. The third component was toluene with 91 qualities. The fourth sample injected was unknown. There were 14

component detected in this sample. From this component, the result was compared with the other three standards. It was found that in the unknown contain the mixture of kerosene and diesel. This was due to the component of p-xylene, o-xylene, and pxylene in the unknown. This component existent is similar to the component detect in the diesel compound. Also component of dodecane, tetradecane and tridecane shows of diesel compound in the unknown. To show the existent of the kerosene compound in the unknown was the detection of compound of benzene 1, 2, 3-trimethyl, benzene 1, 3, 5-trimethyl, benzene 1, 2, 4-trimethyl, which is very similar with kerosene standard. Another compound was found were component of benzene 1-ethyl-2-methyl, benzene 1-ethyl-3-methyl, benzene 1-ethyl-3- methyl. To prove that the unknown has a kerosene compound was the detection of component naphthalene 1-methyl in both unknown and kerosene sample. Conclusion: The hydrolysis of hydrocarbon in common fuels by solid phase microextraction (SPME) and gas chromatography mass spectrometry (GC-MS) was determined and the unknown was a mixture of kerosene and diesel compound. Reference: i. Skoog.D.A. West.D.M. Holler.F.J. Crouch.S.R.(2004). Fundamental of Analytical Chemistry. 8th ed. Thomson Brooks/Cole. Pg 947, 954.