OXIDATION of ISOPROPYL * + e

* + ALCOHOL to ACETONE
6

A Student Experiment
E. C. WAGNER
University of Pennsylvania, Philadelphia, Pennsylvania

I N THE description of a student experiment "The

Fractionating Column in Prepasation of Acetone"
by Robertson,' it is stated that the hot oxidation of
through an unnecessary distillation in the isolation of
acetone in order to appreciate that a column is certain
to be advantageous for such separations.
alcohol by chromic acid "is largely a failure
on account of the continuation of the oxidation to the DIRECTIONS FOR THE HOT OXIDATION OF ISOPROPYL
.
acetic acid-carbon dioxide stage." Oxidation a t 25'
to 40' is accordmgly specified, requiring the mixture
ALCOHOL TO ACETONE

Apwralus: Support a 500sc. ring-neck flask an a stand so

to be chilled in ice after each addition of oxidant. In as t o permit heating with a burner. Adjust t o the flask an a d d -
1926 the writer worked out a student experiment which tion-tube. Through the side arm of the addition-tube pass the
involves the same reaction, the oxidation being effected bent stem of a 250-c~.separatory funnel, and into the vertical
by gradual addition of chromic acid solution to the arm fit a 3-ball Snyder column (or a Vigreux or packed column of
the same size), provided with a thermometer and attached to a
boiling solution of isopropyl alcohol in water. The short condenser. Use as receiver a 200-cc. ring-neck flask. All
reaction is carried out in a flask surmounted by a short the corks of the apparatus must be tight.
fractionating column, through which the acetone is Procedure: Introduce into the reaction flask 25 g. of isopropyl
distilled during and after the oxidation. The crude alcohol and 100 cc. of water. Transfer to the addition-funnel a
cooled solution of 45 g. of sodium dichromate (NaCrZOr2H2O)!
acetone (collected below 65'), and several subsequent 75 cc. of water, and 40 cc. of concentrated sulfuric acid. Heat the
fractions, are redistilled through the column, permitting liquid in the flask just t o boiling, then withdraw the Bame and
the easy isolation of a high yield (70% to 80% or more) add chromic acid solution slowly until boiling is spontaneously
of acetone boilmg 57' to 60' and over 99% pure, and resumed. Continue addition of the chromic acid a t such rate
also the isolation of any unchanged isopropyl alcohol that gentle boiling is maintained, but without active distillation
until about half of the oxidant has been added. Then apply a
(76' to 82'). This procedure involves only two major very small &me, causing acetone t o distil, the temperature a t the
operations and a minimum of manipulation. As i t head of the column not exceeding 60'. When the chromic acid
seems more direct and effective than Robertson's, a solution is all added, distil offthe residual acetone slowly (about
description of the experiment is appended. 30 drops per minute); most of i t passes over below 60". When
this temperature is just exceeded change the receiver (use 50cc.
It is appreciated that Robertson's experiment is de- Erlenmeyer flasks for this and subsequent fractions; stopper and
signed both to illustrate the oxidation of a secondary set aside the flask containing the acetone) and collect in separate
alcohol to a ketone, and to demonstrate the value of a receivers the 60- t o 70- fraction, the 70' t o 85' fraction, and
fractionating column in the isolation of acetone. This finally about 25 cc. above 85". Test the reaction of this aque-
incidental study of the usefulness of a column is evi- ous fraction (?). Note the odor of the steam from the green
liquid in the oxidation flask (?).
dently intended to serve as a substitute for the usual Disconnect the fractionating column and condenser, and dry
experiment on fractional distillation, whose somewhat both of them internally by rinsing successively with alcohol and
artificial character (mixing alcohol and water and ether, and then passing a current of dry air. Adjust the column
"undoing this unnecessary operation") is pointed out. t o the flask which contains the crude acetone, attach the con-
denser and thermometer, and seat the flask in a perforated board.
A careful examination of Robertson's directions, how- Place as receiver a dry 50-cc.Erlenmeyer flask,previously weighed.
ever, reveals the fact that in order to accomplish the and distil offthe acetone slowly (30 drops per minute). When the
double purpose of the experiment the isolation pro- temperature just exceeds 60°, introduce the 60' t o 70° fraction
cedure is made fully as artificial, involving three dis- and redistil, collecting as acetone anything which passes over
tillations from three different flasks, after which the below 60'. Similarly redistil the other fractions so as t o collect
as much as possible of the acetone in the h t receiver, and so as
student will appreciate that he should have used a to separate as a final 76- t o 82" fraction any unchanged isopropyl
column for the first distillation, and it may occur to alcohol.
him to wonder why a product so much distilled should Calculate the yield of acetone on the actual weight of isaprapyl
finally be collected as an 8' fraction (up to 65'). If alcohol used and not recoverable, and take into consideration the
purity of the acetone obtained. The purity of the isaprapyl
he had previously performed an experiment involving a alcohol can be derived from its specific gravity.' Assume the
study of fractional distillation with aid of a small isopropyl alcohol recovered in the experiment t o approximate
c o l ~ m n it
, ~ would not be necessary for him to toil constant-boiling composition (87.9% propanal-2). Determine
- the specific gravity of the acetone, and calculate its purity from
a LANDOLT-BORNSTEIN,
"Physikalisch-Chemisthe Tabellen."
5th ed.. Vol. I, p. 454.
09
the values reported by ICrug."' It should be above 997& The are corrected for the purity of the isopropyl alcohol
yield thus determined should be 75% to 85% of the theoretical. (97.6%) and for that of the acetone, and are calculated
COMMENTS both with and without correction for recovered iso-
Robertson apparently assumes commercial isopropyl propyl alcohol.
Vicrdofaurac
alcohol to be about 90% pure. The Eastman Co. Is* Ncnlrclira Colc.
product used in this laboratory, however, had the 3"-
specific gravity 0.7919 r:), corresponding to 97.6%
propanol-2. It is hence advisable to determine the
Mahod of oxidoiiol
alcohol
rcodcd

Hor Oxidolion, s described: ....

specific gravity of the alcohol used. The amount of 44 g. diehromate 79.4
dichromate specified is a moderate excess, 41.3 g. being Somr:48~.dichromate 17.9 99.7 3.1 75.5 84.9
required by equation. Even with 48 g. of dichromate Cold Oridolion: 25" to
40' (Robertson) 17.3 98.9 1.8 72.5 79.4
some isopropyl alcohol was recovered. As is shown
below, cold oxidation as directed by Robertson leaves In two other trials using hot oxidation the acetone
some isopropyl alcohol unoxidized. It would seem was collected only up to 59'. The yields were then
that in this reaction some over-oxidation can hardly smaller, but the product had the specific gravity of
be avoided, especially near the end, when the mixture pure acetone. I t therefore seems better to extend the
contains little alcohol and much acetone. acetone fraction to 60'. as the yield is higher and the
I n the accompanying table are listed results of four purity still above 99%. In the directions given the
runs, of which three involved hot oxidation and one quantity of dichromate is set at 45 g. somewhat ar-
cold oxidation as directed by Robertson. In all cases bitrarily in absence of definite data as to the effect of
the isolation was effected as described above. Yields excess oxidant upon yield.
- KRUG,2.anal. C h . ,32, 106 (1893).
The assistance of Dr. J. K. Simons and of Benjamin
* Densities of acetone-water mixtures at 20": 100% acetone Einhorn in the trials reported above is appreciatively
0.79197. 95% 0.80748. 90% 0.82197. acknowledged.