In th e La b o r a to r y

An Integra ted Ex tra ction/ Crysta lliza tion/ Distilla tion

Ex periment
Cla ude Am sterda m sk y
Labo rato ire de Chimie O rg anique, ESPCI, 1 0 Rue Vauquelin, 7 5 2 3 1 Paris Cedex 0 5 , France

Mastering extraction, crystallization, and distillation given in Figure 1.

is a prerequisite for efficiency in the organic chemistry labo-
ratory. In most laboratory textbooks (1) those operations are
described separately or used to isolate a final product. A
published procedure in this Journal (2) involves microscale
separation of a five-component mixture in three 3-hour
laboratory periods. However our aim was a shorter exercise
on a standard scale. We therefore propose the separation
and purification of a three-component mixture containing
benzoic acid, 2,2,4-trimethylpentane (isooctane), and meth-
oxybenzene (anisole) plus a trace of picric acid. The separa-
tion can be done during two 4-hour laboratory periods. For
the past three years, this experiment has been carried out
by students in our laboratory with excellent results.
The principal components of the mixture are inexpensive
and nontoxic. Benzoic acid is extracted by an aqueous solu-
tion of sodium carbonate and precipitated through acidifi-
cation. Picric acid imparts a yellowish color to the crude
acid. By recrystallization from boiling water pure colorless
benzoic acid is obtained (mp = 120–122 °C, lit. 122.4 °C [3]).
The liquid components are easily separated by distil-
lation, as 2,2,4-trimethylpentane boils at 99 °C and meth-
oxybenzene at 154 °C. A first crude distillation allows the
students to observe the course of temperature change and to
draw a graph of distillation temperature vs. volume show-
ing the plateau between the two fractions. A careful redis-
tillation yields 2,2,4-trimethylpentane and methoxybenzene
with good purity. A flow chart outlining the procedure is
Benzoic acid
2,2,4-trimethylpentane
Methoxybenzene
Picric acid (trace)
Aqueous Sodium carbonate
Extraction
Sodium benzoate 2,2,4-trimethylpentane
Methoxybenzene
Aqueous
Organic
Concentrated
HCl
Rough distillation
Benzoic acid
Crude
2,2,4-trimethylpentane
Recrystallization
Water Impure
Methoxybenzene
Impure
Benzoic acid
Pure Careful
Distillation
A bulk solution is prepared from 1 L of 2,2,4-trimethyl-
pentane, 1 L of methoxybenzene, 100 g of benzoic acid, and
0.36 g (0.02%) of picric acid; each student receives 50 mL of
the mixture, containing 23.56 g of methoxybenzene, 16.11 g
of 2,2,4-trimethylpentane, 2.32 g of benzoic acid, and ca. 8
mg of picric acid. After extraction and distillation the fol-
lowing results are obtained (Table 1).
Experimental Procedure
Benzoic acid, 2,2,4-trimethylpentane and methoxy-
benzene are not toxic but may cause slight irritation. Gloves
are recommended for mixture handling.
Picric acid is explosive in the dry state. However, the
amount per student is very small (ca. 8 mg), and it is al-
ways in solution; therefore it does not present a significant
danger.
Benzoic Acid Extraction
Fifty milliliters of mixture is transferred to a separa-
tory funnel and extracted twice with 25 mL of a 10% solu-
tion of Na2 CO3 in water, care being taken to vent the sepa-
ratory funnel. Completeness of the extraction can be
checked by extracting a third time and adding concentrated
HCl to the solution; a precipitate of benzoic acid indicates
an incomplete extraction.
The aqueous phases are pooled and acidified to pH 1
by concentrated HCl, and the precipitate is vacuum-filtered
on a Buchner funnel and washed with cold water. Recrys-
tallization of the off-yellow acid in boiling water yields white
crystals of benzoic acid (mp = 122 °C, Kofler hot stage).
Separation of 2,2,4-Trimethylpentane and Methoxybenzene
The mixture remaining in the separatory funnel is
washed with water, decanted into an Erlenmeyer flask,
dried over CaCl2 , and filtered through glass wool. The clear
liquid is then transferred to a distillation flask equipped
with a Vigreux column and heated with an electric heating
mantle. Carborundum chips are added to regulate boiling.
A first rough fractional distillation yields two fractions: A,
with a boiling point below 105 °C, and B, with a boiling
point above 105 °C
A is redistilled, the first fraction being taken below 95
°C, the main fraction between 95 and 105 °C. B is then
added to the cooled distilling flask. An intermediate frac-
tion is taken between 105 and 155 °C, methoxybenzene be-
ing taken between 155 and 160 °C.
Fraction purity can be checked by GC on a packed
Careful
Distillation

Methoxybenzene
Report weight 2,2,4-trimethylpentane Pure Table 1. Results for 108 Experiments
m.pt. Pure
Theoretical Experimental
Yield Yield ± SD Yield Purity
Report weight (g) (g) (%) (%)
Report weight b.pt.
b.pt. G.C. analysis Benzoic acid 2.32 1.49 ± 0.32 64 –
G.C. analysis
2,2,4-Trimethylpentane 16.11 11.68 ± 2.58 72.5 90.2
Figure1. Flow chart for separation of the three-component mixture. Methoxybenzene 23.56 16.21 ± 3.03 68.6 98.7

JChemEd.chem.wisc.edu • Vo l. 7 5 N o . 2 February 1 9 9 8 • Jo urnal o f Chemical Educatio n 219

In th e La b o r a to r y
OV-225 column (5% on Chromosorb W-HMDS 80/100 mesh)
at 80 °C.
Acknowledgments
We thank Delphine Vinclet for her help in testing these
procedures and J. F. Lawrence for reviewing the text.
Literature Cited
1. Fieser, L. F.; Williamson, K. L. Organic Experiments, 5th ed.;
Heath: Lexington, MA, 1983; pp 23–62. Durst, H. D.; Gokel,
G. W. Experimental Organic Chemistry, 2nd ed.; McGraw-Hill:
New York, 1987; pp 74, 84, 95. Most, C. F., Jr. Experimental
220 Jo urnal o f Chemical Educatio n • Vo l. 7 5 N o . 2 February 1 9 9 8 • JChemEd.chem.wisc.edu
Organic Chemistry; Wiley: New York, 1988; pp 77–135.
Harwood, L. M.; Moody, C. J. Experimental Organic Chemis-
try; Blackwell Scientific: Oxford, U. K., 1989; pp 114–121.
Tietze, L.-F.; Eicher, T. Reactions and Syntheses in the Or-
ganic Laboratory; University Science Books: Mill Valley, CA,
1989; pp 23–25. Pasto, D.; Johnson, C. R.; Miller, M. J. Ex-
periments and Techniques in Organic Chemistry; Prentice
Hall: Englewood Cliffs, NJ, 1992; pp 43, 47, 56. Mayo, D. W.;
Pike, R. M.; Trumper, P. K. Microscale Organic Laboratory,
3rd ed.; Wiley: New York, 1994; pp 61, 71, 90. Roberts, R. M.;
Gilbert, J. C.; Martin, S. F. Experimental Organic Chemistry;
Harcourt Brace: Fort Worth, TX, 1994; pp 69, 96, 129.
2. O’Hara-Mays, E. P.; Yuen, G. P. J. Chem. Educ. 1989, 66, 961–
964.
3. Handbook of Chemistry and Physics; Weast, R. C., Ed.; CRC:
Cleveland, OH, 1975; p C-174.