Application Note # CA-273877 Ethanol Content in Denatured Fuel Ethanol According to ASTM D 5501

Introduction
Biofuels have become increasingly important as alternatives to conventional fuels. Examples are biodiesel and bioethanol. Biodiesel is derived from esterification of vegetable or animal fat. Bioethanol is mainly produced by sugar fermentation.The main source of the sugar used for bioethanol production comes from specifically grown crops. These crops include corn, maize and wheat. However, waste straw, willow and poplar trees, sawdust, reed canary, cord and miscanthus grasses, Jerusalem artichokes, and sorghum are also used. Ethanol has a high octane number and was originally intended to replace lead as an octane enhancer. Nowadays, ethanol is blended with gasoline to improve combustion efficiency thereby reducing polluting emissions. The most common blend is 10 % ethanol and 90 % petrol (E10) though the latest vehicles can operate on up to 85 % ethanol and 15 % petrol blends (E85). ASTM D 5501 is the method commonly used to determine the ethanol content of denatured fuel ethanol by gas chromatography. Ethanol is determined from 93 to 97 mass%. Instrumentation: Bruker 450-GC Gas Chromatogarph Injector: 1177 split/splitless, full EFC control Detection: FID with full EFC control Autosampler: Bruker CP-8400 GC Control and Data Handling: Galaxie Chromatography Software Materials and Reagents: Column: CP-Sil PONA CB, 100 m x 0.25 mm x 0.5 m Sample Preparation: A commercially available household methylated spirit or denatured ethanol was used for this application note.

Methanol

Ethanol

TAME

1-Butanol

Benzene

10

15

20

25

Min

30

Figure 1: Chromatogram of a household methylated spirit or denatured ethanol.

Table 1: Response factor according ASTM D 5501. Mass relative response factor Methanol Ethanol 3.20 2.06

Results and discussion

Figure 1 shows a chromatogram of denatured alcohol obtained using the condtions set out above. The calculation of the mass% of ethanol and methanol is done using a normalized area percent calculation with response factors. In order to show the suitability of the system, repeatability was tested. According to ASTM D 5501, two successive results may exceed 0.21 % only once every 20 analysis. Figure 2 shows the data set from 36 successive runs and the limits specified. The same approach was taken for the determination of the methanol content of the sample. In Figure 3, 15 successive runs are shown, again with limits specified in ASTM D 5501. Figures 2 and 3 show that the data never exceeded the levels specified in the method.

Conditions
Carrier Gas: Helium, 40 psi Injector: 250 C, split 1:200 Injection Volume: 2 L Oven: 15 C (12 min) @ 30 C/min to 250 C (19 min) Detection: 300 C

Ethanol content mass % 95.5

95.0

94.5 0 5 10 15 20 25 Run 30

Figure 2: Repeatability of ethanol content with limits specified by the method.

Methanol content mass %

3.40 3.35 3.30 3.25 3.20 0 5 10

Run

15

Figure 3: Repeatability of methanol content with limits specified by the method.

Conclusion
The data presented here clearly show the suitability of the system for accurate determination of ethanol and methanol according ASTM D 5501.

Keywords Ethanol ASTM D 5501 Denatured Fuel Ethanol Gas chromatography

Instrumentation & Software 450-GC Gas Chromatograph CP-8400 Autosampler Galaxie Chromatography Software

References
ASTM Standard D 5501, 1994, Determination of Ethanol Content of Denatured Fuel Ethanol by Gas Chromatography, ASTM International, West Conshohocken, PA, www.astm.org

Authors: Arno Woltering

For research use only. Not for use in diagnostic procedures.

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to change specifications without notice. Bruker Daltonics 12-2010, #CA-273877