A QuantitativeGas Chromatographic Ethanol

Determination
A Contemporary Analytical Experiment
James J. Leary
James Madison University, Harrisonburg, VA 22807

This note describes a gas chromatographic experiment for

the quantitative determination of volume wercent ethanol in
water ethanol solutions. Since its introdukion in 1974, approximately 40 analytical chemistry students per year have
successfully performed this experiment. The samples studied
contain only two components, ethanol and water. For this
reason, a simple calihration curve is very well suited for the
accurate determination of volume percent ethanol over a wide
concentration range. Experiments illustrating the use of other
methods for quantitative gas chromatographic determination
have also recently been described: internal standard plus
calibration curve ( I ) , standard addition plus corresponding
plot (21, and relative response factor methods ( 3 , 4 ) .The accuracy and precision of the results of this experiment are both
on the order of 2.0%. The precision with which students can
measure the peak areas off the chromatograms is the limiting
factor.
Experimental

Four standards are prepared in 50-ml volumetric flasks by

diswensinz 10.00. 20.00. 30.00, and 40.00 ml of ethanol with
a h k e t and diluting to &lume'with water. Volume % ethanol
= (volume ethanolltotal volume) * 100.
Approximately 1WLof the standards and unknowns are
infected into the chromatopra~h.Sarn~lesize and attenuation
are varied so that all peaks are at least 40 mm high. Chart
speed is adjusted such that the water peak is about 20 mm
wide a t half height.
The experiment has always been performed using 'I4 in. od.
X % meter Porapak' T1 columns, 80-100 mesh, installed in
Gow Mac gas chromatographs equipped with thermal conductivity detectors; however, any chromatograph with thermal
conductivity detectors could he used.2
A calibration curve is constructed usine area ethnnoll1area
~
-,~ ~
ethanol + area water) as the dependent variable and volume
percent ethanol as the independent variable. In addition to
the experimentally determined points, the calihration curve
should include the known noints (0.0)
. . and 1100.1).
. . . The volume
percent ethanol in the unknowns is determined via the calibration curve. (Unknowns are prepared in the same manner
as the standards.)
Students are told that n roof is by definition two times the
volume percent ethanol at 60F (5).They are also told that
real world samples should readily suggest themselves, and that
they are welcome to analyze their own samples of alcoholic
beverages and compare their results with the concentrations
of ethanol given onthe labels.
~

~~

Results and Discussion

VII I l t h l l l l

Area ethanollWea ethanol

+ area water) versus volume percent ethanol

seeing straight line calibration curves. There are at least two

reasons for the curvature. First, a thermal conductivity detector is a mass sensitive device; therefore, ratio of peak areas
becomes approximately proportional to weight percent ethanol. In general, weight percents and volume percents are not
linearly related. Second, a curve m i ~ hhe
t anticiwated because
any concentrated solutions, volumes are not additive, meaning
that volume (total) f volume (ethanol) + volume (water).
A final point involves an extension of this experiment in
which students have used least squares computer programs
to fit the data associated with this experiment. Because the
slope of the curve is changing slowly, and because there are
no inflection points, a second order polynomial of the form y
= a*. h r 2 is a very acceptable model for the curve. No y intercept term is necessary because the curve must pass
through the point (0,O). In the case of the data presented in
the figure, the resulting line is given by the following equation, ~
~
~
~
.

where y is the area ratio and n is the volume percent ethanol.

Acknowledgment

The author wishes to acknowledge R. C. Atkins for providing the instrument operating instructions used a t JMU;
T. G. Leahy, superintendent, A. Smith, Bowman Distillery,
Sunset Hills, VA, for much helpful advice concerning methods
for the preparation of standards and alternate methods for
the determination of volume percents; and F. A. Palocsay,
with whom I co-authored a meeting presentation ( 6 ) on a
virtually identical take-off experiment applicable at the
freshman level.

The figure illustrates a typical calihration curve. The fact

Literature Cited

iz) van~ t t * R., E. and van~

'

Porapak" is a registered trademark of Waters Associates, Inc.,

Maole Street. Milford. MA.
? lnsrr~ments
equpped wjlh flame#on,?allondetectors cannot oe
"SW oecau5e F D s 00 not respond to walcr

~~~

~..

,~~

t tR.~L.,, J. CHEME ~ ~57,230

~ . (1980).
.
(31 Karasek,F. W..DeDecker, E. H.,Tiernay.J. M . , J CHEM. EDUC.51.816 (1974).
14) Pacer. R.A,. J. CHEM.EDUC..
53,582 (1976).
15) Hawley, Gessner C., "The Condensed Chemical Dietionsrv: 8th ed.., Van Nostrand
ReinholdCo.,New York. 1971, p. 732.
(6) Pelocsa%F.A.,sndLesm, J. J.,psper2d7Soufbeast-Southwe~tRegj
jdAcSMeeting,
Memphis,TN,

1975.

Volume 60 Number 8 August 1983

675