Experiment 2 – Analysis of Hydrocarbons

Using Gas Chromatography

Experiment 2

Analysis of Hydrocarbons Using Gas Chromatography

An important source of the world’s energy comes from hydrocarbons. Natural sources of
hydrocarbons originate from petroleum, natural gas, and coal, which are then chemically
converted to provide fuel, electrical energy, and heating. In this experiment, a technique called
chromatography will be used to analyze some of these hydrocarbons. Chromatography is a
powerful separation method that separates mixtures of compounds into their components which
can be further qualitatively deduced to characterize and identify them. This technique can also
be used for quantitative analysis by determining how much of each component is present in the
mixture. In this experiment, gas chromatography – one of the most important branches of
chromatography – will be used to qualitatively identify these hydrocarbons and a mixture of
hydrocarbons will be quantitatively analyzed to determine the mixture’s individual components.

Gas Chromatography (GC) is a very well established separation technique for the identification
and quantification of materials that can be presented in a volatile state without decomposition.
Chromatographic methods are based on the types of mobile and stationary phases and the
kinds of equilibrium involved in the transfer of solutes between phases. A carrier gas acts as a
transport vehicle known as the mobile phase. This mobile phase is then forced through an
immiscible stationary phase (or substrate), held on a solid support material which is either
coated on the inside of a capillary column or held on particulate packing within a column. The
continuous motion of the carrier gas causes components of the gas to separate. Each
component then moves at a different rate through the GC column due to different retardation
effects of the stationary phase. Finally, the presence of the components is detected by the
detector as they leave the column.

The time taken for a sample between the injection and its appearance at the detector is called
the retention time. The retention time is a reflection of the degree of retardation of the sample
by the column and is a column specific value. Moreover, the retention time also depends on the
flow rate of the carrier gas (i.e., how hard the sample is being pushed through the column) and
the temperature of the column. If any of these parameters are changed, then the retention time
will also change. A comparison of retention times is a method for the qualitative analysis of an
unknown sample.

If a detector that responds to solute concentration is placed at the end of the column and its
signal is plotted as function of time, a series of peaks is obtained by a chart recorder (or similar
device) connected to the GC. Such a plot is called a chromatogram. The position of peaks on
the time axis may serve to identify the components of the sample; areas under the peaks
provide a quantitative measure of the amount of each component.

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 Experiment 2 – Analysis of Hydrocarbons
Using Gas Chromatography

Chemical Reagents:
Hydrocarbons Solvents
• n-heptane  Isopropanol
• n-hexane  Methanol
• iso-octane (2,2,4 trimethylpentane)
 n-nonane
 n-octane
 n-pentane
• unknown – mixture of hydrocarbons

Glassware and apparatus:

• 7 – 1 mL Mohr pipets and bulb
• 7 – 5 mL volumetric flasks

Instrument and equipment:

• Varian Saturn 2200 Gas Chromatograph
• Syringe – 10.0 μL in 0.05 units with flat needle
• Capillary column: Elite-5; 30 m length and 0.32 mm i.d.

Procedure

Note: This procedure must be performed in the fume hood!

Part I: Preparation of Solutions

1. Obtain six vials of the samples of hydrocarbons and six 5 mL volumetric flasks.

2. Label the volumetric flasks with the names of the hydrocarbons for easy
identification.

3. Pipet 1 mL of hydrocarbon into the volumetric flask and dilute with solvent using a
Pasteur pipet for a total of 5 mL:

Hydrocarbon Solvent

n-Pentane
n-Hexane Methanol
n-Heptane

Isooctane
n-Octane Isopropanol
n-Nonane

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 Experiment 2 – Analysis of Hydrocarbons
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4. Repeat the above procedure in preparing the hydrocarbon solutions, using a new
pipet to measure the 1 mL of hydrocarbon into the volumetric flask.

5. Transfer a small volume of the solutions to a labeled vial.

Note: Bring only the transferred solutions in vials to the instrument area. Large
quantities, like those in the volumetric flasks, are susceptible to spillage and
possibly contamination of the instruments.

Part II: Repeatability and Accuracy

The GA will demonstrate the proper procedure on how to perform a GC injection.

Do not attempt to do an injection before the GA does a demonstration.

An important technique in obtaining consistent results is determined by consistent injections.

Each student will perform three injections until the retentions times for each peak are within ±
0.1 seconds of each injection and the “Result” are within 5% between injections.

Activate Method:

1. Click on Inject in the toolbar and then Inject Single Sample.

2. Type in your name under Operator and click Yes. Double-click on Default Sample
(first cell in table) and enter “Heptane – Run 1”. Click Inject when finished.

3. Wash the 10 µL syringe by drawing up the n-heptane mixture halfway up the syringe.
Eject the contents onto a Kimwipe. Repeat three times for a thorough cleaning.

4. Measure 1 µL of the n-heptane mixture on the syringe. Observe carefully to ensure

no air bubbles are present when the solution was drawn up. Eject the contents onto
a Kimwipe and repeat the measurement if any air bubbles are noticed.

Note: Air is very harmful to a GC system. Ensure there are absolutely no air
bubbles present in the syringe prior to injection.

After measuring 1 µL into the syringe, pull up the plunger until the bottom of the
plunger sits between 5 – 6 µL.

5. View the screen to observe if a green Ready circle is indicated next to “Running”. It
should not read “Monitoring” or “Stabilizing”.

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 Experiment 2 – Analysis of Hydrocarbons
Using Gas Chromatography

6. Slowly insert the needle into the injection port until the bottom of the barrel cannot
continue and press down the syringe to start the run.

Note: Since this is a split injection, quickly push the plunger down to eject all of the
sample. If it was a splitless injection, the contents would be released slowly.

7. Bring the syringe back up, but leave the needle in the injection port for a few seconds
before removing it. (Why?)

8. Perform two additional runs by repeating the above steps (entering the Default
Sample as “Heptane – Run 2” and “Heptane – Run 3”) until the retention times are ±
0.1 seconds from each other.

Data Analysis:

1. Which peak is the solvent (methanol) and which peak is the n-heptane? How was
the differentiation between the two peaks made? Identify and label the two peaks on
the chromatogram.

2. Submit the chromatograms and its corresponding results by clicking on

• View/Edit Chromatogram
• View Results Only

3. Calculate the solvent efficiency, column efficiency, and the number of theoretical
plates for each chromatogram. Discuss and compare the results of these
calculations.

Part III: Split Ratios and Sample Injections

This section of the experiment demonstrates how closing the split vent (splitless injection) and
then opening the split vent (split injection) affects the n-hexane peak.

Activate Method:
Split Ratio Off

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 Experiment 2 – Analysis of Hydrocarbons
Using Gas Chromatography

1. Click on Inject in the toolbar and then Inject Single Sample.

2. Type in your name under Operator and click Yes. Double-click on Default Sample
and enter “Hexane – SR off”. Click Inject when finished.

3. Wash the 10 µL syringe by drawing up the n-hexane mixture halfway up the syringe.
Eject the contents onto a Kimwipe. Repeat three times for a thorough cleaning.

4. Measure 1 µL of the n-hexane mixture on the syringe. Observe carefully to ensure

no air bubbles are present when the solution was drawn up. Eject the contents onto
a Kimwipe and repeat the measurement if any air bubbles are noticed. After
measuring 1 µL into the syringe, pull up the plunger until the bottom of the plunger
sits between 5 – 6 µL.

5. View the screen to observe if a green Ready circle is indicated next to “Running”. It
should not read “Monitoring” or “Stabilizing”.

6. Slowly insert the needle into the injection port until the bottom of the barrel cannot
continue and press the barrel down to start the run. To release the contents, slowly
inject the sample into the injection port. Bring the syringe back up, but leave the
needle in the injection port for a few seconds before removing it.

Note: Since this is a splitless injection, the contents would be released slowly.

7. Repeat the above steps by increasing the split ratios:

Activate Method:
Split ratio 25

Split ratio 50

Split ratio 75

Split ratio 100

Data Analysis:

1. What observation can be made with the split ratio turned off?

2. What is observed with respect to the peak area, peak height, and resolution when
the split ratio is increased?

3. Submit chromatograms and the results. Identify the solvent and hydrocarbon and
their corresponding peaks. Also, identify the retention time and area for each peak.

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 Experiment 2 – Analysis of Hydrocarbons
Using Gas Chromatography

Part IV: Characterization of Selected Hydrocarbons

When performing integrations for Part IV, do not include or label the methanol peak in the Peak
Table or chromatogram.

A. Analysis of Short Chain Hydrocarbons

Activate Method:

1. Review instructions from Parts II, Steps 1-8 before beginning this section. Repeat,
but this time for n-pentane.

2. Inject 1 µL after washing the syringe and setting up the software to be “Ready” for
the next run.

3. Repeat the above steps for 1 µL of n-hexane and 1 µL of n-heptane.

Note: Remember to wash the syringe with methanol in between injections of

sample and in between injections of hydrocarbons.

B. Analysis of Long Chain Hydrocarbons

Activate Method:

Repeat the instructions as state above (“Analysis of Short Chain Hydrocarbons”) with 1 µL
injections of iso-octane, n-octane, and n-nonane.

Note: Remember to wash the syringe with isopropanol in between injections of

sample and in between injections of hydrocarbons.

Data Analysis:

Since GC separations are based on (among other things) boiling point differences in
compounds, the compound with the lowest boiling point usually elutes first and has the shortest
retention time. Provide a chart of the hydrocarbons and their respective boiling points. Do the
retention times of the hydrocarbon peaks correspond to when they should elute from the column
and be detected? If not, provide an explanation as to why the hydrocarbons eluted from the
column in that order.

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 Experiment 2 – Analysis of Hydrocarbons
Using Gas Chromatography

Part V: Identification of Unknown Mixture

An unknown mixture will be qualitatively and quantitatively analyzed under the same conditions
as previous procedures. The unknown will contain two of the hydrocarbons used in Part IV.

1. The method used will be determined by which solvent the unknown dissolves in best.

If the sample dissolves in methanol, activate

If the sample dissolves in isopropanol, activate

2. Inject 1 µL of the sample and repeat the analysis for a total of three trials. Do not
include the methanol peak in the integrations.

Data Analysis:

Submit the chromatograms with the two alkane peaks identified. Report their percentage
composition and show all calculations. Describe a more accurate way in calculating percent
composition for multiple injections.

Calculations:

Calculate the parameters used to characterize the efficiency of a separation: the number of
theoretical plates (N) and height equivalent to a theoretical plate (HETP).

Questions

1. Why is it necessary to wait for all peaks to be recorded before a different sample can
be injected? Discuss in terms of retention times and bandwidths.

2. List three specific laboratory uses for this instrumental technique. Include a brief
discussion of the accuracy of such techniques. Also include at least one
environmental application.

3. Can all organic samples be analyzed using this technique? Why or why not? What
types of samples are best analyzed by this technique?

4. Sometimes using retention times is not sufficient for qualitatively identifying

compound as it comes off a GC column. Name three instruments that can be used
in conjunction with a GC for more definitive compound identification.

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 Experiment 2 – Analysis of Hydrocarbons
Using Gas Chromatography

5. A homologous series of primary alcohols is to be determined by GC. Given that the

retention for ethanol is three minutes and 1-propanol is four minutes, predict the
retention times for 1-hexanol, 1-butanol, and 1-pentanol.

6. Compare iso-octane and octane retention times and explain discrepancies.

References

1. Cassidy, R. F., J. Chem. Ed., 1976, 53(1), 51.

2. Dal Nagore, S. and Juvent, R. S., Gas-Liquid Chromatography, Theory and Practice,
Interscience, New York, 1962.

3. Official Methods of Analysis of the Association of Official Analytical Chemists, 15th

edition. Leddy Library call number: Reference S 587 .A74.

4. Robinson, James W., Undergraduate Instrumental Analysis, Marcel Dekker, Inc., New
York, 1970.

5. Sawyer, D. T., Heineman, W. R. And Beebe, J. M., Chemistry Experiments for

Instrumental Methods, John Wiley & Sons, Toronto, 1984.

6. Skoog, Douglas A., Principles of Instrumental Analysis, 7th edition, Saunders College
Publishing, Toronto, 1984, pp. 757-783.

7. "Hydrocarbons for the 21st Century - The Work of the Loker Hydrocarbon Research
Institute". Nobelprize.org. http://nobelprize.org/nobel_prizes/chemistry/articles/olah

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 Experiment 2 – Analysis of Hydrocarbons
Using Gas Chromatography

Laboratory Report and Marking Scheme

Deadline: Groups III and IV: Week of Feb. 2nd, 2011 @ the beginning of the lab session.
Groups I and II: Week of Feb. 16th, 2011 @ the beginning of the lab session.

0. Title Page: Include:

 Title of experiment
 Student’s name and ID number
 Lab partners’ names
 Lab section
 Date of submitting lab report

1. Abstract (2 marks)

2. Purpose

3. Theory: Gas Chromatography (5 marks)

 Discuss the importance of hydrocarbons and the role each hydrocarbon plays as
an energy resource.
 Describe the components of a GC system:
 carrier gas
 sample injection system (discuss split ratios)
 column (discuss types and differences)
 oven
 detector (discuss types and differences)
Include a schematic diagram of a GC system

 State the applications of GC (examples)

 Describe and/or explain mobile and stationary phases; name/state examples of
the two phases
 Describe and/or explain what occurs when stationary phases are solid and liquid
 why is the analyte retained?
 List the variables that must be achieved or controlled to achieve optimal
resolution.
 Explain
 the importance of resolution (definition and what it is affected by)
 importance of column efficiency
 retention time (definition and what it is dependent on)
 Explain solvent efficiency, column efficiency, and theoretical plates

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 Experiment 2 – Analysis of Hydrocarbons
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3. Procedure: any changes (additions/deletions) to the procedure should be noted here.

4. Results and Calculations: (6 marks)

Part II: Repeatability and Accuracy (2 marks)

 Calculations should include:

 average retention time and the standard deviation of the retention time.
 average area of the peaks and the standard deviation of the area.
 Must include chart with results of retention time and peak area, and an
explanation on what these results indicate. Do the results demonstrate the
accuracy and repeatability of GC experiments done?
Must include table, calculations, and chromatograms for full marks.

Part III: Split Ratios and Sample Injections (1 mark)

 Include table that contains results – retention time and peak area
 Briefly describe findings and what information do the chromatograms provide:
what was observed with respect to peak area, peak height, and resolution when
the split ratio was increased?
Must include table and chromatograms for full mark.

Part VI: Characterization of Hydrocarbons (1 mark)

 Include chart that shows the retention times of samples and their peak areas.
The average area should be determined and the standard deviation of the area
should be calculated for the six hydrocarbons.
 Briefly state what the data predicts:
 Does the general trend follow the longer the alkane, the longer the retention
time?
 Does the peak area vary inversely with hydrocarbon length in which the
longer the chain, the smaller the peak area?
Must include table and chromatograms for full mark.

Part V: Identification of Unknown Mixture (2 marks)

 Include table of results which includes compound name, retention time, peak
area, and % peak area for each of trial of the two unknowns.
 Calculations should be included to show how the percentage composition of the
two compounds in the mixture was determined. State how the denominator (the
sum of all the corrected peak areas) is determined when calculating the
percentage composition.
Must include table, calculations, and chromatograms for full marks.

5. Accuracy (5 marks)

6. Discussion: no human errors should be included (3 marks)

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 Experiment 2 – Analysis of Hydrocarbons
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7. Conclusion: (1 mark)

 state composition of both unknowns

 was the relationship between peak area and sample volume linear?
 did retention times increase with an increase in carbons?
 did gas chromatography prove to be an accurate technique?

8. Questions (2 marks)

9. References (1 mark)

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 Experiment 2 – Analysis of Hydrocarbons
Using Gas Chromatography

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