Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

10/27/15
Drawer No.

Course / Section

#21

CHEM
315/204

Purpose:
The purpose of this experiment is to identify an unknown organic compound based on its retention
time via gas chromatography and calculate the molar percentage of compounds in a mixture based on
their relative peak areas.

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

10/27/15
Drawer No.

Course / Section

#21

CHEM
315/204

Approach:
Using the gas chromatograph, Obtain a chromatogram for a standard equimolar solution of four
esters (Ethyl acetate, Propyl acetate, Butyl acetate, and Pentyl acetate) and determine the retention times
for each compound. Obtain a second chromatogram for an unknown mixture of the aforementioned
esters and determine the retention times for each compound. Calculate the peak areas for each
chromatogram. Using the values collected from the standard equimolar solution; adjust the peak area
values of the unknown solution for thermal response. Calculate the total area from adjusted area
values. Calculate mole fraction for each ester present in the unknown solution. Calculate mole
percentage for each compound from the mole fraction.
References
Text
Pavia, D.L., Lampman, G.M., Kriz, G.S., Engel, .G.R., 2011, Introduction to Organic Laboratory
Techniques, A Small Scale Approach, GMU Edition, Chem 315/318, Cengage Learning: pp. 817-836
Slayden, S., Stalick, W., Roth, R, 2014, Organic Chemistry Laboratory Manual, 2nd Edition:
Pearson Custom Publishing: pp. 51-54
Web Site URL
Dr Schornicks Website: http:/mason.gmu.edu/~jschorni/gaschromatography
Unknown or Synthesized Compound
Ethyl acetate, 141-78-6, CRC Handbook of Chemistry & Physics, 84th Edition, Lide, D.R., Editorin-chief, 2003-2004, CRC Press, p 3-250, 4871.
Propyl acetate, 109-60-4, CRC Handbook of Chemistry & Physics, 84th Edition, Lide, D.R., Editorin-chief, 2003-2004, CRC Press, p 3-468, 9203.
Butyl acetate, 123-86-4, CRC Handbook of Chemistry & Physics, 84th Edition, Lide, D.R., Editorin-chief, 2003-2004, CRC Press, p 3-80, 1487.
Pentyl acetate, 628-63-7, CRC Handbook of Chemistry & Physics, 84th Edition, Lide, D.R., Editorin-chief, 2003-2004, CRC Press, p 3-440, 8662.

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

Proc # 1

Gas Chromatography

Materials

2L
Standard ether
sample

2L
Unknown ether
sample
Desc:

Equipment

Gas
chromatography

microsyringe

Begin a new chromatogram.

Rinse the microsyringe several times
with the sample solution.

Insert the syringe into the sample

solution and raise and depress the plunger
several times to remove any air bubbles from
the syringe.

Load the microsyringe with a small

amount of sample (2L).

Insert the syringe into the

chromatograph port through the rubber
septum.

Quickly inject the sample and

withdraw the syringe from the port

Wait approximately 5 minutes to

allow the sample to be analyzed.

Print resulting chromatogram.

Rinse the syringe with the sample

solution several times.

Repeat steps with additional samples.

Equation Setup:

10/27/15

Results

Drawer No.

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#21

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315/204
Unk No.

Instrument Readings
Injection port temp.
120oC
Column temp.
120oC
Detector temp.
120oC
Chart Speed
25.0mm/min
Gas flow rate
10 mL/min (He @ 7PSI)
Moving liquid phase
Supelco Carbowax 20m, 6 ft
Observations:
Acetone was not used to rinse the syringe to
prevent residual/incorrect readings.
Complete reading of compound took
approximately 5 minutes.

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

Proc # 2

10/27/15

Retention Time

Drawer No.

Course / Section

#21

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315/204

Results

Materials

Equipment

Desc:

Calculator

Chart Speed = 25.0mm/min

Retention Times Standard Solution
Peak Distance (mm) Retention Time (min)
C2
37.0
1.48
C3
45.5
1.82
C4
64.0
2.56
C5
94.5
3.78

Computed from the chart speed and the

distance on the chart from the time of injection
to the point on the chart when the perpendicular
line drawn from the maximum pen deflection
intersects the base line.

Mark starting point on chart (t = 0)

Draw vertical line from peak top to base R.T.C2 = 37.0 / 25.0 = 1.48
line
R.T.C3 = 45.5 / 25.0 = 1.82

Measure distance from starting point to

each peak.
R.T.C4 = 64.0 / 25.0 = 2.56
Equation Setup:
R.T.C5 = 94.5 / 25.0 = 3.78
Where v = velocity, d = distance, and t = time:

Therefore, where t= retention time:

Retention Times Unknown Solution

Peak Distance (mm) Retention Time (min)
C2
----C3
46.0
1.84
C4
68.5
2.74
C5
----R.T.C3 = 46.0 / 25.0 = 1.84
R.T.C4 = 68.5 / 25.0 = 2.74

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

Proc # 3

Peak Area

Chromatograp
hs for known and
unknown solutions

Drawer No.

Course / Section

#21

CHEM
315/204

Results

Materials

10/27/15

Equipment

Ruler
Calculato
r

Desc:

Measure the height of the peak (in

mm.) from the baseline

Measure the width of the peak at half

the height

Multiply the two measurements to

determine the peak areas.
Equation Setup:
Where h = peak height from baseline and
width of peak at the peak height:

Peak Areas-Standard Solution

Peak

Height (mm)

C2
C3
C4
C5

176
171
149
132

(mm)
5
6
7
8

Peak Area (mm2)

88
103
104
106

AreaC2 = 176 * 5 = 880

AreaC3 = 171 * 6 = 103
AreaC4 = 149 * 7= 104
AreaC5 = 132 * 8 = 106
Peak Areas-Unknown Solution

=
Peak

Height (mm)

C2
C3
C4
C5

0
59
97
0

AreaC3 = 59 * 6 = 35
AreaC4 = 97 * 7 = 68

(mm)
0
6
7
0

Peak Area (mm2)

0
35
68
0

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

Proc # 4

10/27/15

Adjusted Peak Areas

Materials

Desc:

Course / Section

#21

CHEM
315/204

Results
Equipment

Drawer No.

Calculator

*It is assumed that the unknown mixture is missing

Ethyl acetate (C2) and Propyl acetate (C3) will be
used for the basis of the calculations.
Adjusted Peak Area

Thermal response factors (TR) are

C3
C4
computed as ratios of the areas of one peak in
Peak Area (mm2)
103
104
Standard
TRs/TRi=As/Ai
the known mixture (base peak) to the area of
1.00
1.01
(s=C2 )
each of the other peaks in the mixture
2
Peak Area (mm )
35
68

There must be at least two similar

Unknown
A1/As
1.00
1.96
(s=C2)
compounds in the known and unknown
mixtures
Standard Solution:

TR values will be calculated from the

areas under the peaks in the standard equimolar TR3 = AreaC3/ AreaC3 = 103 / 103 = 1.00
mixture.
TR4 = AreaC4 / AreaC3 = 104 / 103 = 1.01
Equation Setup:
Where s refers to the base peak (ethyl acetate), I
refers to the number of carbons in each component
in the mixture, area refers to the peak area
measured, and TR refers to the thermal response
factor:

TR5 = AreaC5 / AreaC3 = 106 / 103 = 1.03

Unknown Solution:
AAC3 = (35 / 35) * 1.00 = 1.00
AAC4= (68 / 35) *1.01 = 1.96

AA= Adjusted Area

C5
106
1.03
0
0

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

Proc # 5

10/27/15

Total Peak Area

Course / Section

#21

CHEM
315/204

Results

Materials

Desc:

Drawer No.

Equipment

Total Peak Area

Calculator

The areas of gas chromatogram peaks

are proportional to the molarity of the
compound.

Varying thermal conductivity based on

the structure and substituent groups of different
compound causes deviations in this relationship

Determined from the adjusted peak areas

and add them to determine the total peak area
Equation Setup:
Add adjusted peak area values calculated for each
of the components of the solution to determine the
total peak area.

A1/As
(s= 2)

EtAc (2)

ProAc (3)

BuAc (4)

PtAc (5)

1.00

1.96

0
= 2.96

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

Proc # 6

Mole Fraction

Desc:

Drawer No.

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#21

CHEM
315/204

Results

Materials

10/27/15

Equipment

Calculator

Mole Fraction: Unknown

1.00 / 2.96

Computed by dividing the individual

adjusted peak areas by the sum of the adjusted
peak areas in the chromatogram.

Equation Setup:
Where areai represents a component of the mixture and
represents the adjusted total peak area:

1.96 / 2.96

0.338

0.662

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

Proc # 7

10/27/15
Drawer No.

Course / Section

#21

CHEM
315/204

Mole Percent

Results

Materials

Equipment

Desc:

Computed by multiplying the Mole

fraction values by 100.

Represents the percentage of moles of a

component that is present in a compound.
Equation Setup:

Mole Percent

Calculator
ProAc
BuAc

Mole Fraction
0.338
0.662

x 100 =
x 100 =

Mole %
33.8
66.2

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

10/27/15
Drawer No.

Course / Section

#21

CHEM
315/204

Summary of Results:
The injection port temperature was 120 oC. The column temperature was 120oC. The detector
temperature was 120oC. The gas flow rate was 10mL/min. The chart speed was 2.5cm/min. The
moving liquid phase was SUPELCO CARBOWAX 20m, 6ft. The retention times for the standard ester
solution were as follows: C2=1.5; C3=1.8; C4=2.6; C5=3.8. The retention times for the unknown ester
solution were as follows: C3=1.8; C4=2.7. The peak areas for the standard ester solution were as
follows: C2=8.80; C3=10.3; C4=10.4; C5=10.6. The peak areas for the unknown ester solution were as
follows: C3=3.50; C4=6.80. The thermal response factors for the standard ester solution were as
follows: TR3=1.00; TR4=1.01; TR5=1.03. The adjusted peak areas for the unknown ester solution were
as follows: AAC3=1.18; AAC4=2.33. The total adjusted peak area for the unknown ester solution was
2.96. The mole fractions for the unknown ester solution were 0.338 and 0.662. The mole percentages
for the unknown ester solution were 33.8% and 66.2%.

Analysis & Conclusions:

Gas chromatography is used to separate and analyze organic compounds that can be vaporized
without decomposing. It is a useful technique for determining both the quantity and the identity of a
compound(s) in a solution.
This analysis assumed that the detector was equally sensitive to all organic compounds and responded
in a linear fashion. As such, the area from the baseline of a gas chromatogram to a peak represents the
number of moles of a compound present in a solution. It, however, is not valid to assume that peak area
and number of moles are directly proportional for every organic compound. To increase the accuracy
of this measure, a chromatogram of a standard equimolar solution of similar compounds must first be
measured and analyzed. This preliminary measurement can be used to calculate the Thermal
Response factor for each component of the unknown solution and adjust the measurements for the
unknown compound accordingly.

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

10/27/15
Drawer No.

Course / Section

#21

CHEM
315/204

The separation of esters by the gas chromatograph was based on the differences in boiling points (and
thus the vapor pressures) of each of the compounds. Compounds with lower boiling points typically
display shorter retention times because they have higher vapor pressures and spend more time in the
vapor phase than they do in the liquid phase. This validates that the first peak furthest to the left (the
peak with the shortest retention time) on the chromatogram for the standard ester solution represents
Ethyl acetate, as it had the lowest boiling point and was the most volatile of the fours esters in the
solution and the shortest retention time (C2=1.5). It is also safe to assume that each subsequent peak
represents the ester before it +1C, as the more carbon atoms a molecule contains correspond to a
higher boiling point and a higher molecular weight. This is only reasonable when the components of a
solution of alkenes are very similar in structure (i.e. contain similar functional groups like the acetates
analyzed).
The number of moles for each compound on the chromatograms was determined based on the
measured areas beneath each peak. The standard solution contained approximately 1 mol of each
ethyl, propyl, butyl and pentyl acetate.
After identifying each peak for the standard equimolar mixture, the retention times were compared to
those of the unknown chromatogram. The distance of the peaks on the unknown chromatogram were
closest to that of the peaks that represented propyl acetate and butyl acetate. This is a sound conclusion
as all other conditions of the chromatograph remained constant for both readings.

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

10/27/15
Drawer No.

Course / Section

#21

CHEM
315/204

Literature Summary (Unknowns, Synthesized Compounds)

Unknown No.
CAS No.
Name (IUPAC)

141-78-6

109-60-4

123-86-4

628-63-7

Ethyl acetate

Propyl acetate

Butyl acetate

Pentyl acetate

Synonyms

Acetic acid ethyl

ester; Acetic ether;
Acetoxyethane;
Ethyl Acetic Ester;
Ethyl ethanoate

Acetic acid propyl

ester

1-Acetoxybutane,
Butyl ethanoate

Melting Point
(oC)

Lit -83.8oC
Exp

Lit -93.0oC
Exp

Lit
Exp

-77.0oC

Lit
Exp

Boiling Point
(oC)

Lit 77.1oC
Exp

Lit 101.0oC
Exp

Lit
Exp

126.0oC

Lit 149.4oC
Exp

Lit 1.382825
Exp

Lit
Exp

1.394120

Lit 1.402320
Exp

Refractive Index Lit 1.372320

(nD20)
Exp

Amyl acetate

-61.0oC

Solubility
(Rel to Water)

Lit s
Exp

Lit sl
Exp

Lit sl
Exp

Lit sl
Exp

Density
Rel to Water

Lit 0.900320g/cm-3
Exp

Lit 0.882025g/cm-3
Exp

Lit 0.882520g/cm-3
Exp

Lit 0.875620g/cm-3
Exp

Molecular
Formula

Structural
Formula

C4H8O2

C5H10O2

C6H12O2

C7H14O2

Experiment:

Date:

Gas Chromatography: Acetates

Name

Partners

Katheryn Soto

N/A

10/27/15
Drawer No.

Course / Section

#21

CHEM
315/204