1114 CHAPTER 37 Selected Methods of Analysis
PROCEDURE
Step 1. Prepare approximately 1 L of 0.05 M NaOH. Standardize this solution
against weighed portions of dried primary-standard potassium hydrogen
phthalate (KHP); use about 0.4-g (to the nearest 0.1 mg) samples of KHP
for each standardization.
Step 2. Record the number of tablets in your sample. Transfer the tablets to a
clean 500-mL volumetric flask (Note 1). Dissolve them in a minimum
volume of 3 M HCl (4 to 5 mL/tablet should be sufficient). Then dilute to
the mark with distilled water.
Step 3. Titrate the free acid in several 15.00-mL aliquots of the dissolved sample;
phenolphthalein is a satisfactory indicator.
Step 4. Condition the column with about 15 mL of 3 M HCl (Note 2), followed by
three 15-mL portions of distilled water. Never permit the liquid level to
drop below the top of the column packing.
Step 5. Charge each column with a 15.00-mL aliquot of the sample. Elute at a rate
of about 2 to 3 mL/min. Wash the column with three 15-mL portions of
water. Collect eluate and washings in a conical flask. Repeat this step with
additional aliquots of the sample (Note 3).
Step 6. Titrate the eluted samples (and washings) with standard base. Correct the
total volume for that needed to titrate the free acid, and calculate the mass
of Mg(OH)2 in milligrams in each tablet.
Notes
1. The sample will dissolve more quickly if the tablets are first ground in a mortar.
If you choose this alternative, you will need to know (a) the total mass of your
tablets and (b) the mass of ground sample that you transfer to the volumetric
flask.
2. The volume of the sample aliquots and the volume of base used in the several
titrations must be measured carefully (to the nearest 0.01 mL). All other vol-
umes can and should be approximations only.
3. A 25-mL buret packed to a depth of about 15 cm with Dowex-50 cation
exchange resin makes a satisfactory column. Reconditioning after 4 or 5 elu-
tions is recommended.
37R GAS-LIQUID CHROMATOGRAPHY
As noted in Chapter 31, gas-liquid chromatography permits the analyst to separate
the components of complex mixtures. The accompanying directions are for the
determination of ethanol in beverages.
37R-1 The Gas-Chromatographic Determination of
Ethanol in Beverages15
Discussion
Ethanol is conveniently determined in aqueous solutions by means of gas chro-
matography. The method is readily extended to measurement of the proof of
alcoholic beverages. By definition, the proof of a beverage is two times its volume
percent of ethanol at 60°F.
15Adapted from J. J. Leary, J. Chem. Educ., 1983, 60, 675.
37R Gas-Liquid Chromatography 1115
The operating instructions pertain to a 1/4-in. (o.d.) 0.5-m Poropack column
containing 80- to 100-mesh packing. A thermal conductivity detector is needed.
(Flame ionization is not satisfactory because of its insensitivity to water.)
The determination is based on a calibration curve in which the ratio of the area
under the ethanol peak to the area under the ethanol-plus-water peak is plotted as a
function of the volume percent of ethanol:
vol EtOH
vol % EtOH 100%
vol soln
This relationship is not strictly linear. At least two reasons can be cited to account
for the curvature. First, the thermal conductivity detector responds linearly to mass
ratios rather than volume ratios. Second, at the high concentrations involved, the
volumes of ethanol and water are not strictly additive, as would be required for lin-
earity. That is,
vol EtOH vol H2O vol soln
PREPARATION OF STANDARDS
Use a buret to measure 10.00, 20.00, 30.00, and 40.00 mL of absolute ethanol into
separate 50-mL volumetric flasks (Note). Dilute to volume with distilled water, and
mix well.
Note
The coefficient of thermal expansion for ethanol is approximately five times that
for water. It is thus necessary to keep the temperature of the solutions used in this
experiment constant to 1°C during volume measurements.
PROCEDURE
The following operating conditions have yielded satisfactory chromatograms for
this determination:
Column temperature 100°C
Detector temperature 130°C
Injection-port temperature 120°C
Bridge current 100 mA
Flow rate 60 mL/min
Inject a 1-L sample of the 20% (v/v) standard, and record the chromatogram.
Obtain additional chromatograms, adjusting the recorder speed until the water peak
has a width of about 2 mm at half-height. Then vary the volume of sample injected
and the attenuation until peaks with a height of at least 40 mm are produced. Obtain
chromatograms for the remainder of the standards (including pure water and pure
ethanol) in the same way. Measure the area under each peak, and plot
areaEtOH/(areaEtOH areaH2O) as a function of the volume percentage of ethanol.
Obtain chromatograms for the unknown. Report the volume percentage of
ethanol.
1116 CHAPTER 37 Selected Methods of Analysis
WEB WORKS
Material Safety Data Sheets (MSDSs) are an important resource for anyone using
chemicals. These documents provide essential information on the properties and
toxicity of chemicals that are used in the laboratory. Go to http://chemistry
.brookscole.com/skoogfac/. From the Chapter Resources menu, choose Web
Works. Locate the Chapter 37 section, and click on the link to a comprehensive list-
ing of most of the Internet sites that present MSDSs. Go to one of the sites and look
up the MSDS for oxalic acid. Browse through the entire MSDS, read the reactivity
data, note its chemical properties, and find the first-aid treatment for ingestion of
oxalic acid. Chemical manufacturers are required by law to furnish an MSDS for
every chemical that they sell, and many of them can be found on the Internet. It is a
good idea to examine the MSDS for any substance that you use in the laboratory.
