Determination and quantification of benzene and toluene in gasoline

using gas chromatography and flame ionization detector(FID).

Michael Strandell ITM, Stockholm University . RUPP 23 Januari 2006

Background.
Urban air has of wide range of different pollutants. Here is a short description of some
that is of interest for the organic analytical chemist.

Particulate matter.
Particulate matter is a mixture of coarse and fine organic and inorganic substances,
present in the atmosphere as both solids and liquids. Coarse particles have a diameter of
more than 2.5 µm and fine particles less than 2.5 µm. Particles are often referred to as
PM10 which means they have a diameter of less than 10µm. The main sources of
particulates are industry, vehicles and domestic coal burning.The particles also contains
low volatile organic compunds like polyaromatic hydrocarbons(PAH).

Volatile Organic Compounds (VOC).

VOCs include a very wide range of individual substances, such as hydrocarbons,
halocarbons and oxygenates. All VOCs are compounds of carbon and exist as
atmospheric vapeurs. Hydrocarbons include benzene, xylene and toluene.

Benzene
Benzene is a volatile organic compound, i.e. it readily evaporates. About 80% of human
made emissions come from petrol fuelled vehicles. The major effect of benzene from
chronic(long term) exposure is to the blood. Benzene damages the bone marrow and can
cause a decrease in red blood cells leading to anemia. It can cause excessive bleeding and
depress the immune system. Benzene is also a carcinogenic. To avoid long term (chronic)
effects including cancer, the guideline for benzene is 0.37 parts of benzene per billion
parts of air (ppb), averaged over a year. In Stockholm(Sweden) the levels are generally
between 1 to10 ug/m3. 1ppb = 1.16 ug/m3. In vehicle exhaust the source of benzene is a
combination of dealcylation of toluene and the benzene present in the fuel. In Europe
and the USA the levels of benzene in gasoline is from 0.3% and up to the maximum of
2%.

Toluene
Toluene, also known as methylbenzene or phenylmethane is a clear, water-insoluble
liquid with the typical smell of paint thinner, reminiscent of the sweet smell of the related
compound benzene. It is an aromatic hydrocarbon that is widely used as an industrial
feedstock and as a solvent.Toluene is used as an octane booster in fuel, as a solvent in
paints, paint thinners, chemical reactions, rubber, printing, adhesives, lacquers, leather
tanning, disinfectants, and to produce phenol and TNT. It is also used as a raw material
for toluene diisocyanate, which is used in the manufacture of polyurethane foam.

Benzene. B.P. = 80.1 degrees. S.G.=0.8786 g/cm3

Toluene B.P.= 110.6 degrees S.G.=0.8669 g/cm3

Xylene B.P. = 144 degrees S.G.= 0.86 g/cm3

Hexane B.P.= 69 degrees S.G.= 0.6548 g/cm3

Separation and detection

The determination of benzene and toluene will be done using gas chromatography
equipped with flame ionization detector and using o-xylene as surrogate standard. The
detector is coupled to a computerized integration system which will be used for the
evaluation. Analysis will be carried out on both gas phase and liquid phase. For the
headspace(gas phase) analysis the GC will run isothermal at a temperature of 30 degrees
in order to separate low boiling hydrocarbons. Each run is 10 minutes. For the analysis of
the liquid phase the GC will run as follow:
Initial temp 30 degrees, initial time 2 minutes then 10 degrees/minute to 50 degrees, final
time 2 minutes.
Injection technique will be split with a split ratio 1:30. The column is a 15 meter x 0.32
mm DB5 with 0.25um phase thickness. Carrier gas is hydrogen.

Preparation.
Remember the the quality of the final result depends on how accurate the
samples and standards are prepared.

Retention and response factor standard.

Add 20 ul of benzene, toluene and o-xylene respectively to 1 ml hexane. Use a micro
pipette.

Samples
Add 50 ul of gasoline and 20 ul of o-xylene to 1 ml of hexane. Do this for each gasoline
in separate test tubes. Use micro pipette.

Analysis.
1) Do a headspace analysis of all the gasoline. Use a 25 ul syringe and withdraw 20 ul of
the gase phase above the petrol. Do not dip the needle in to the gasoline.

2) Inject ca 0.1 ul of the retention standard. Use air plug only, no other solvents in the
syringe.

3) Inject ca 0.1 ul of each sample as above.

If the signal during analysis gets to high(>1 Volt) dilute the samples with 1 ml hexane.
 Identification
Standard
Use the standard to identify the different compounds. Remember that they will elute in
boiling point order. Integrate the peaks and fill in the table with retention time, the
relative retention time to the surrogate standard and the peak areas. The areas will be used
later in the calculation.

Samples(liquid phase)
Identify and integrate the three relevant peaks in each sample. Start with the surrogate
standard peak. Then use the relative retention times identified from the run of the
standard sample to find relevant peaks. Integrate and write down area, retention time and
relative retention time.

Samples(gas phase).
Identify benzene and toluene. Why does the gas phase look so different?
Can you see any difference in the patterns between different gasoline?

Quantitation.
Definitions:

Analytes(x): unknown compounds

Standard(s): known compound. Used for identification and calculation.

Surrogate standard(ss): A standard with known concentration added as early as

possible in the analytical process. Used for identification and quantitation of the analytes.

External standard(es): A standard with known concentration added after the clean up
and before injection. Used for calculation of the recovery of the analytes.

Respons factor(rf). An amount/area factor that dependends on how well the detector
actually reacts to the analyte. The rf also depends on how well the chromatography
works e.g. injector,column and detector.

Relative response factor(rrf). The quota between rf for the standard and rf for the
analyte. rrf for the surrogate standard is always 1.

Area(a). The integrated area of a peak.

Concentration(C).
1) Start to calculate rf and rrf for the analytes. Use rf = A/amount and rrf = rfss / rfx

2) Since we do not know the actual specific gravity of the different gasoline we will use
volumes instead of weights. In general you would convert volumes to weights.

Concentration of the analytes is calculated as below:

Cx = Ax / A ss x Css x rrfx
If we had an external standard added we would just have compared the areas of SS and
ES and thus calculated the recovery of our standard. This is importand since it would tell
us how well our clean up method works.

Sample table
Sample Retention Relative Area Concentration. Response Relative Calculated
time(rt) retention factor(rf) response concentration
time(rrt factor(rrf)