Rose M.

Lanes
and Donald G. Lee1
Pacific Lutheran University
Tacoma, Washington 98447
I Chromic Acid Oxidation of Alcohols
I
A simple experiment on reaction rates

Despite the emphasis that a number of
modern organic chemistry textbooks place on the effect
of substituents on reaction rates there is a general
scarcity of simple laboratory experiments that can be
used to illustrate this phenomenon. I n an attempt to
improvise such an experimentwe have found the chromic
involved initial formation of a chromate ester which
then underwent decomposition by a two-electron
transfer with cleavage of the a-carbon-hydrogen bond
being the rate determining step; i.e.,
K
-
n

acid oxidation of substituted ethanols, X-CH2CH20H, RCHZOH + H,CrO, 3

fast
RCH2OdrOH + H,O
I1
(1)
to be well suited for this purpose. This reaction has
the following advantages: (1) during the course of the
reaction the solution undergoes a definite color change
(bright yellow to pale green) that permits the progress
of the reaction to be followed visually, (2) the rates are
subject to large changes when the electronic nature of
the substituents is varied, (3) the rates can be adjusted
to give a convenient reaction time simply by changing
the acidity of the reaction medium, (4) the entire -
fast II
experiment can be carried out using equipment that is 2CrY + 2RCH=OH-+2Cr1" + RCH (4)
readily available in the average laboratory, (5) it is a
(Aldehydes are also susceptible to oxidation by chromic
well known and important reaction with a readily
acid but under the conditions of the present experi-
available literature (1-7), (6) an understanding of the
ment where the primary alcohols are present in excess
mechanism of the reaction does not require an advanced
little second stage oxidation would occur.)
knowledge of organic chemistry on the part of the The students were also told, in order to prevent them
student, and (7) the results present the students with a from falling into a trap, that the effect of substituents
set of facts that demand an explanation and that en-
on the equilibrium step (1) was not great. This is well
courage many to pursue some further reading and illustrated in the table by comparing the exact oxidation
independent thought.
rates for the alcohols (which were determined spectro-
I n the experiment, as it was used here, pairs of stu- photometrically by one of us, R. M. L., as part of an
dents determined the relative rates of oxidation by undergraduate research project) with the equilibrium
adding exact quantities of each alcohol to a solution of
constants, which are available in the literature. It was
chromium(V1) in dilute sulfuric acid and visually
also stressed that since step (2) is rate determining the
monitoring the course of the reaction. Since it was not
effect of suhstituents should be explained in terns of
possible to add all of the alcohols simultaneously, the
carbon-hydrogen bond cleavage and electron transfer.
rates of only two substituted ethanols could be compared
Since the exact explanation of the effect of substitu-
during any one run. However, since the number of ents on this reaction is still a matter of some doubt, the
alcohols used was not large, the number of runs required
laboratory reports, as well as a subsequent examination
to organize the total group in order of increasing rate of
question based on this experiment, were graded on the
reaction was not burdensome. I n fact, most students
coherence of the discussion rather than on the basis of
found it a challenge to amange the alcohols in the correct
any "correct" explanation. The decrease in reaction
order using the least possible number of runs. rates observed for those alcohols bearing electron with-
All of the students (the experiment has been used to
drawing suhstituents is difficult to reconcile with a
date with over seventy students) were easily able to
proton transfer step. On the other hand, although
determine the correct order of reactivity in one labora-
more reasonable on the basis of these results, it is appar-
tory period (2.5 hr); however the interpretation of the
ent that a simple hydride transfer step is not acceptable
results required more effort. I n a pre-laboratory either: Oxidants which effect hydride transfers attack
conference certain features of the reaction were de-
ethers readily (lo), but chromic acid does not oxidize
scribed. I n particular, the work of Westheimer and
most ethers a t an appreciable rate (11).
his coworkers in establishing the reaction sequence by
A more satisfactory interpretation of the observed
use of induced oxidations and deuterium labeling was
results is that electrons are transferred from carbon to
discussed (1). Their work showed that the reaction
chromium via a cyclic transition state, IV, that can be
realized by any one of three possible electron flows;
'Author to whom inquiries should be sent at the Department I (representing hydride transfer), I1 (representing
of Chemistry, University of Saskatchewan Regins Campus, proton transfer), or I11 (representing homolytic cleavage
Regina, Saskatchewan, Canada. of the carbon-hydrogen bond) (2,12).
Volume 45, Number 4, April 1968 / 269

On the basis of this model the type of electron transfer
would be determined by the degree of overlap of the
carbon-hydrogen-oxygen and the carbon-oxygen-chro-
mium orbitals in the transition state and could be de-
pendent on the nature of R. I n any case, introduction
of electron withdrawing substituents into the structure
of the alcohol would make it more reluctant to release
its electrons to chromium(V1) and thus reduce the rate
of reaction.
As can be seen from the table the rate of oxidation of
methanol is abnormallv low. This has also been noted
by RoEek (IS) and & probably a result of the low
reactivity of a methyl group as compared to methylene
groups. Hence it seems best, to us, not to include
methanol in the series of alcohols employed for this
experiment.
Oxidation of Substituted Ethonols bv Chromic Acid
[alcohol] = 9.23 X 10-P M; [H$Od = 3.56 M; [KCrzOd =
3.56 X lo-"; Temperature = 25.0 =t 0.1"C
Alcohol k, (sec-I). C,. b i n )
a Pseudo first order rate constants.
a Equilibrium constant for ohromate ester formation.
Glycol concentration reduced to 4.62 X lo-' M.
Reference (8).
Reference (7).
Although we have used this reaction solely as a
demonstration of substituent effects on rates it is
probable that it could be used to illustrate other rate
phenomena as well. For example, a comparison of the
rates a t different acidities or different temperatures
could be used to show acid catalysis and temperature
effects on reaction rates.
Experimental
Determinotion of Relative Rater
Each pair of students first prepared an oxidizing solu-
tion by addition of about 0.5 g of sodium dichromate di-
hydrate and 50 ml of concentrated sulfuric acid to 200ml
of water. After allowing it to cool to room temperature,
each student carefully filled a 10 ml graduated cylinder
to the mark with the bright yellow chromic acid solution.
He then secured exactly 3.0 ml of a 0.40 M solution of
one of the alcohols in a 15 X 125 mm test tube, and his
partner similarly obtained a diierent alcohol. (The
alcohol solutions were prepared prior to the laboratory
period and dispensed from 50-ml burets. Mouth-sucked
pipets should not be used because some of the alcohols
are detrimental to ones health if ingested.) When all
270 / Journol of Chemical Education
was ready, the two partners simultaneously added the
chromic acid solutions to the alcohols, stoppered the
test tubes, shook them briefly and proceeded to deter-
mine the relative reaction rates by a comparison of the
intensity of color in each tube a t intervals. They then
repeated the procedure with as many different pairs as
required to arrange all of the alcohols in order of in-
creasing ease of oxidation.
The alcohols which gave us the best results were
1-propanol, ethanol, 2-methoxyethanol, 2-chloroethanol,
and 2,2,2-trifluoroethanol. We also experimented
with the use of 3-chloro-1-propanol but abandoned it
because it was too difficult to purify and because good
pseudo first order kinetics were not obtained when the
exact rate was determined spectrophotometrically.
Ethylene glycol can also be used if the concentration is
halved to compensate for the presence of two hydroxyl
groups in this molecule, hut 1,3-propanediol reacts
abnormally fast because it can form a cyclic diester
with chormic acid (14).
Although it was not absolutely necessary we found it
helpful to provide each group of 20 or 30 students with a
colorimeter so that they could occasionally verify
electronically what they were observing visually.
(A wavelength of either 350 mp or 444 mp can be used.)
Actually the only instance in which it is necessary to
consider using instrumentation is with the ethanol-
propanol pair. Since the rates for these two vary by
only about 25%, it is sometimes difficult to be certain
which solution is changing more rapidly.
KL
Exod Rote Meosurementr
The exact rates reported in the table were determined
using a Beckman DU spectrophotometer fitted with
a thermostated cell compartment. The oxidation
medium was prepared by addition of 1.00 ml of a
3.91 X M solution of potassium dichromate to
10.0 ml of 3.91 M H2SOP. Aliquots (3.00 ml) of
this solution were then pipetted into 1.00-cm cells
which were thennostated at 25.0 1 O.l°C for several
minutes. An excess of alcohol (2.77 X lo-* moles)
was added from a microliter syringe fitted with a
Chaney adaptor, and the reaction rates were followed by
noting the absorbance (350 mp) a t intervals of time.
The pseudo first order rate constants were then obtained
from a plot of log absorbance against time. All of the
alcohols were purified by fractional distillation before
use.
Acknowledgment
The authors are pleased to acknowledge several
helpful discussions with Drs. Laurence Huestis and
Charles Anderson.
Literature Ciled
(1) WESTHEIMER, F. H., Chem. Rev., 45, 419 (1949).
(2) STEWART, R., "Oxidation Mechanisms," W. A. Benjamin,
Inc., New York, 1964, p. 3 7 4 8 .
(3) WIBER~,K. B., in "Oxidation in Organic Chemistry"
(Edilw: WIBER~,K. B.), Academic Press, Inc., New
York, 1965, p. 142 ff.
(4) WATERS,W. A,, "Mechanism of Oxidation of Organic Com-
pounds," John Wiley & Sons, Inc., New York, 1964, p.
588.
(5) HOUSE, H. O., "Modern Synthetic Reactions," W. A.
Benjamin, Inc., New York, 1965, p. 7E90.
(6) ROBERTS,J. D.,AND CASERIO, M. C., "Basic Principles of (9) STEWART, R., AND LEE, D. G., Unpubli~hedresults.
Organic Chemistry," W. A. Benjamin, Inc., New York, (10) BARTER,R. M., AND LITTLER,J. S., J . Chem. Soe., (B), 205
1965.. .
0. 401-405. (1967).
(7) LEE, D. G.,in "Oxidation: ~ ~ ~and Application
h ~ in
i ~ (11)~ BROWNELL,
~ , R., LEO,A., CAANQ, Y. w., AND WESTHEIMER,
Organic Synthesis," (Editw: Augustine, R. L.) Marcel F. H., J . Am. Chem. Soe., 8 2 , 406 (1960).
Dekker, Inc., New York, in pms. (12) STEWLILT, R., AND LEE,D. G., Can. J . Chem., 42,439 (1964).
(13) R O ~ E KJ.,, Coll. Czech. Chem. Comm., 25, 1052 (1960).
(8) KLXNINQ,U., AND M. C . R., J . Chem. Soc., 3204
SYMONS, (14) R O ~ E KJ.,, AND WESTHEIMER, F. H., J . Am. Chem. Soe., 84,
(1961). 2241 (1962).

Volume 45, Number 4, April 1968 / 271