Muriel E.

Finlayson
and Donald G. Lee I Oxidation of Ethanol by ~ h r o m i u m ( ~ l )
I
University of Saskatchewan
Regina, Canada A kinetics experiment f o r freshmen

T h e oxidation of alcohols by chro-
mium(V1) is a reaction of considerable importance and
has been widely studied (1, 2). The progress of the
reaction can be follo~ved visually or spectrophoto-
metrically because the color of the solution changes
from orange (HCrOa-) to green (Cr3+) (3). AS a con-
sequence of this dramatic color change it has found
application in the Breathalyzers presently being used
throughout Canada. A measured volume of a person's
breath is passed into a standardized chromium(V1)
solution and any ethanol present reacts according to
eqn. (1).
We have found that the experiment is one in which
students have a good deal of interest and which gives
clear cut results without the necessity of using equip-
ment more elaborate than a pair of burets. Results
obtained by an experienced demonstator are plotted in
Figure 1; a typical student's results are plotted in
Figure 2. After using this experiment with a large
number of students we have observed that only 2'3,
fail to identify the reaction as being first-order in
HCr04-. I n addition to sewing as an introduction to
the subject of kinetics, this experiment provides
students with practice in the use of a large number of
skills including weighing, titrating, preparation of
standard solutions, standardizing solutions, and han-

The decrease in absorbance is then a direct measure of

the amount of alcohol present in his lungs. Con-
sequently, this is a reaction with which some freshman
students have had experience and in which most are
often more than passively interested. It is therefore,
in terms of the current vernacular, a reaction with
relevance. Furthermore, we have observed that it can
successfully be used to teach some of the basic prin-
ciples of kinetics.
Specificallywe asked our students to follow the rate of
reaction titrametrically and to determine the order of
the reaction with respect to HCrOn-. I n a pre-
laboratory conference it was pointed out that the com-
plete rate law for the reaction was of the form
V = k,lHCrO,-l*[CHsCH~OHl'[H+l'
However, under conditions where the concentrations
of ethanol and acid are large (and therefore approxi-
mately constant during the reaction) the rate law
reduces to V = k[HCrOa-1". The problem is then t o I I
10
I
20
I
30
I
40
I
50
I
60
I
70
I
80
determine a value for x (0, 1, or 2) by following the rate Time (rnin)
of reaction titrametrically (see experimental section for
Figure 1. Kinetic d ~ t aobtained by an experienced worker. The ordi-
details) and by making the appropriate rate plots note has "nib of l/mole for the second-order plot, moler/l for the rero-
(4, 6). order plot and dirnenrionlerr logarithmic "nib far the flrrt-order plot.

Volume 48, Number 7, July 1971 / 473

 an analytical balance and make up the solution in a 500-ml
volumetric flask. Calculate the concentration of HCrOd-
present in the solution.
3. Rinse and fill an acid buret with the HCr04- solution.
Rinse and fill a base buret with NsnSIOa sqlution (supplied
in the laboratory).
4. Fmm the acid buret measure exactly 10.00 ml of HCrOd-
solution into a clean 250-ml erlenmeyer flask. Add 4 ml of
3% asueous XI which will reduce HCrOl- and turn the
saintidn red-brown.
2HCrO.- + 61- + 14H+ 4 312 + 2Cr8+ + 8HzO
(oran@) (brown) (green)
Titrate with S n A 0 3 6duli011 to a peel) color and add 2 ml
of 10C; aqueous T h y d e ~ ~(which
e' qhould turn thp aolution
dnrk blue,. Conrinuc titratinp, to a pie blurgreeu end
point. The reaction here is
In + 2S%Os'- + 21- + SrOs+
5. 1Jving the rwo balanced c q u a t i o ~ in
~ i itep 4, the valrulnted
molarity of H ( W i and thc volww of Ka,S90r solution r c
quircd to rnlure 10.011ml oi H(:rO),i wlutim, rnlculnre the
I I I I I I I I I concentration of the Na2S10zsolution.
10 20 30 40 50 60 70 80 6. Using a graduated cylinder measure 200 ml of the HCrOl-
solution into a 250-1111 erlcnmever flask. Then usine a. volu-
Time (min) metric pipet add 2.0 ml of ah"s01ute ethanol and Gix well.
Figure 2. Typisol student rerults. The ordinate has units of I/mols for the Note the time of addition; it will be the sera time for this
recond-erder plot, mobs/\ fw the zer-rder plot and dimemionless experiment. The concentration of HCrOa- a t zero time
logarilhmic unitr for the Rrrt-order plot. will, of course, be that calculnted in step 2.
7. Rinse and fill the acid buret with this CPH~OH:KCI~O,:
dling of stoichiometric equations. We have found that HC1 mixture.
8. Refill Na,SlOs buret and repeat titrstions (step 4) every 10
it fits in well a t the end of a one-semester course. min for 80 min.
9. Summarize your ~xperimentaldata as H rahlc giviug t l ~ e
Experimental Section lime and a,rrwpordiw, volumes of NaAOa and conrcutra-
tions, log&of wnwatration, and reviprocsl* of rlncrrtlra-
Essentially the students were asked to prepare a tions of HCrOl-.
solution of HCrOp-in 3.6 IMHCl, add some ethanol to it, 10. Plot each function ([HCrO,i], log[HCrOl-I and I /
and follow the rate of reaction by titrating an aliquot [HCrO,-1) against time on the same piece of graph psper
every ten minutes for 80 min. They then prepared and identifv the best straight line thereby establishing the
order of the reaction with L ~ e c to t HC&
plots of [HCr04-1, log [HCr04-] and l/[HCr04-] 11. Calculate the rate constant for the reaction and the initial
against time to determine if the order of the reaotion rate of reaction, assuming it to be fimt-order in ethanol and
with respect to HCr0,- was 0, 1, or 2. Specifically in [H+].
they were given the following experimental procedure.
Literature Cited
I. Prrp~lre500 ml of 3.6b t HCL in a graduated 600-ml heakrr.

-
2. Prepare 500 ml of -0.0037 A1 K2ChOlrn 3.6 .If HCl (1% (1) W m m m ~ x s s F.
, H., Chsm. RBD.,45. 419 (1949).
(2) STEWART. R.. "Oxidation Mechanisms." W. A. Benjamin, Inc.. New
lute solutions of K2Crr0, dissociate in aqueous acid as fol-
lows: Crr07" +
H~10 2HCrOl-.) Weigh the K2Cr10Ton
York. 1964, pn. 37-48.
(3) L m e s , R. M., ~ x LBE,
o D. G., J. CHEX. EDUO., 15, 269 (1968).
(4) G-Y. H. B.. A N D H A I ~ X T
G,. P.. JR.. "Basic Prinoiplea of Chemistry,''
W. A. Benjamin. Ino., New York, 1967, pp. 360-1.
1 Available from the Fisher Scientific Co., Montreal. Soluble (5) L ~ e a u o x ,W. H., AND P A R ~ O N T.~ D..
, "General Chemistm." John
starch can he used a s an alternative. Wilay & Sona,Inn., New York, 1966, D. 119.

474 / Journal of Chemical Education