RESEARCH NOTE
A MODIFIED PROCEDURE FOR ALCOHOL DETERMINATION BY
DICHROMATE OXIDATION
E. A. Crowell and C. S. Ough
Department of Viticulture and Enology, University of California, Davis, California 95616.
Presented at the Annual Meeting of the American Society of Enologists, July 27, 1978, San
Diego, California.
Manuscript submitted June 5, 1978.
Revised manuscript received September 15, 1978.
Accepted for publication October 3, 1978.
ABSTRACT
The chemical oxidation method for alcohol deter-
mination in wine after microdistillation of the samples
is used routinely in many winery laboratories. How-
ever, analysts often experience a n u m b e r of difficulties
with the procedure, including use of the distilling ap-
paratus and indicator endpoint when dichromate is ti-
trated with ferrous a m m o n i u m sulfate. The procedure
was modified to avoid some of the problems. Five ml of
wine were distilled in a Cash volatile acid still, oper-
Accurate and rapid determination of ethyl alcohol
in wine is the most important analysis made in winery
laboratories, and the one made most often. A n u m b e r of
studies have described the use of dichromate oxidation
of alcohol as a m e a s u r e m e n t of its content, supplanting
to a degree specific-gravity m e a s u r e m e n t with pyc-
nometers or wine alcohol hydrometers.
The chemical procedure commonly involves adding
a measured volume of standard potassium dichromate
in sulfuric acid solution to a volume of a wine distillate,
allowing the oxidation to occur, and t i t r a t i n g un-
reacted dichromate with ferrous a m m o n i u m sulfate
and a redox indicator, 1,10-phenanthroline. Guymon
and Crowell (3) showed the procedure to be comparable
in accuracy to more tedious pycnometric methods.
Z i m m e r m a n n (5) recommended using a micro-steam-
distillation apparatus requiring only I ml of wine sam-
ple, and Morrison and Edwards (4) described an auto-
mated distillation apparatus for a micro-dichromate
procedure. Caputi et al. (2) cited causes for errors in
these procedures and recommended t h a t auto-diluters
be used for m e a s u r i n g the l-ml wine sample and t h a t
spectrophotometric m e a s u r e m e n t of the chromic ion
formed be the basis of alcohol determination instead of
titration of unreacted dichromate.
The chemical method for alcohol, as outlined by
Amerine and Ough (1), is used routinely for analysis of
wines produced at the University's experimental win-
ery. It has become clear, however, t h a t the procedure
often leads to unacceptable results, particularly when
carried out by r e l a t i v e l y inexperienced laboratory
workers. The primary sources of errors appear to be
61
Am. J. Enol. Vitic., Vol. 30, No. 1, 1979
ated to ensure complete condensation and recovery of
alcohol distillate in a 50-ml volume. Two ml of distil-
late were oxidized at 60°C with 10 ml of dichromate
solution (34 g potassium dichromate plus 325 ml sul-
furic acid per liter). Alcohol concentration was deter-
mined spectrophotometrically at 600 nm, according to
Caputi et al. [Am. J. Enol. Vitic. 19:160-5 (1968)]. The
method as modified provided acceptable speed, preci-
sion, and accuracy for routine analysis of wine alcohol.
manipulation of a l-ml wine sample and of the micro-
distillation, and proper noting of the titration endpoint
with ferrous a m m o n i u m sulfate. The modifications
suggested by this study include use of a 5-ml wine
sample distilled in a Cash volatile-acid still, and spec-
trophotometric m e a s u r e m e n t of chromic ion according
to Caputi et al. (2).
MATERIALS AND METHODS
Stock solutions were prepared from absolute ethyl
alcohol by dilution with distilled water to provide 8, 10,
12 and 14 volume % alcohol-water mixtures. These, in
turn, were diluted 1:10 with water for 0.8, 1.0, 1.2, and
1.4 volume % working standards.
Dichromate solution containing 34 g reagent-grade
potassium dichromate plus 325 mi concentrated sul-
furic acid per liter was prepared according to Caputi et
al. (2).
Five ml of wine sample or stock alcohol standard
solution, equilibrated at 20°C, were pipetted into the
inner chamber of a Cash volatile-acid still and steam-
distilled over 10-15 minutes to collect 30-35 ml of dis-
tillate in an ice-water-cooled 50-ml volumetric flask.
The distillate was directed to the bottom of the flask
and into a few ml of cold water using a Pasteur pipet
connected to the delivery tube of the still. Since the
s t a n d a r d h e a t i n g element of Cash stills provides a
too-vigorous distillation rate, the line voltage supplied
to the element should be reduced with a variable power
transformer. The distillate, representing a 1:10 dilu-
tion of sample, was diluted to exactly 50 ml after tem-
perature equilibration in a 20°C water bath.
62 - - ALCOHOL DETERMINATION
Ten ml of dichromate solution were transferred to
15-ml screw-cap test tubes with an Oxford pipetter.
Two ml of wine distillate or diluted alcohol standard
were added by pipet, and the mixture was capped,
thoroughly mixed, and placed in a 60°C water bath for
20 minutes. After heating, the tubes were cooled in any
convenient water bath. Chromic ion formed from al-
cohol oxidation was m e a s u r e d at 600 nm using a
Bausch and Lomb Spectronic 710 spectrophotometer
equipped with a micro flow-through cell system and
digital readout photometer reading transmittance, ab-
sorbance, or concentration units.
A linear relation was shown between chromic ion
absorbance at 600 nm and alcohol content of the four
stock solutions, steam-distilled 1:10 as wines were.
Used t h e r e a f t e r for routine analysis were a single
working standard, usually the one containing 1.2 vol-
ume % alcohol without distillation, and an appropriate
reagent blank. The photometer concentration readout
was then set to 12.00 for the 1.2 volume % standard,
and the alcohol in a test sample was read directly in
volume % concentration units. In practice, a number of
wine samples, 18-20, can be distilled and held for di-
chromate analysis as a single batch. Using the flow-
through spectrophotometer cell, this number plus nec-
essary standards can be easily handled through the
oxidation and final alcohol determination.
RESULTS AND DISCUSSIONS
The precision of the dichromate method as modified
was tested by distilling six replicate samples of an
alcohol-water solution and of three dry table wines.
The alcohol determinations in each distillate are given
in Table 1. The data show t h a t the method is precise
enough for most winery routine alcohol determination
needs.
Table 1. Precision of modified dichromate method for alcohol.
Samples No. of Alcohol
reps. (volume %)
Min. Max. Mean
Alcohol-water 6 11.72 11.95 11.88
Table wines
1 6 9.37 9.51 9.44
2 6 11.49 11.85 11.61
3 6 13.66 13.79 13.75
The procedure was tested for recovery of added al-
cohol by very carefully mixing 50.0 ml of the table wine
sample no. 1, mean alcohol content 9.44 volume %,
with 50.0 ml of the 14 volume % stock alcohol standard.
Triplicate samples, of the wine and of the wine plus
added alcohol, were distilled and analyzed with this
modified dichromate procedure. The mean alcohol con-
tent of the wine was 9.47 volume %, which agrees well
enough with the value of 9.44 given in Table 1. The
wine-alcohol m i x t u r e contained a m e a n content of
11.62 volume %, relative to a calculated value of 11.72,
representing 99.1% recovery of added alcohol.
Am. J. Enol. Vitic., Vol. 30, No. 1, 1979
An assortment of wine samples were analyzed by
this procedure and compared with determinations by
hydrometer after distillation. The samples included
three dry white table wines, three dry red table wines,
one each of white and red port-types, and a 12-year-old
baked sherry. For hydrometry, 200 ml of tempera-
ture-equilibrated wine was distilled, slowly at first,
into an ice-chilled receiver, collecting about 198 ml.
The distillate was re-equilibrated at the same temper-
ature, and the volume was adjusted with w a t e r to
exactly 200 ml. The alcohol content was carefully de-
termined by hydrometer after standing 24 hours in a
60°F room so t h a t little t e m p e r a t u r e correction of the
readings would be needed. Dichromate and hydrometer
values are given in Table 2. For the dichromate proce-
dure, only three ml of the ports and the sherry were
distilled instead of the five ml used for table wines.
Differences of _+0.2 volume % are a c c e p t a b l e for
routine analysis, and no real trend is apparent in the
direction of the differences.
Table 2. Comparison of dichromate method with hydrometer for
alcohol determination in different wine types.
Wine type Volume % alcohol Difference
Hydrometer Dichromate
Dry white 1 12.4 12.3 + 0.1
2 12.8 12.6 +0.2
3 11.2 11.0 +0.2
Dry red 1 12.8 12.9 - 0.1
2 10.9 11.0 -0.1
3 11.5 11.7 -0.2
White sweet 20.8 20.8 0.0
Red sweet 19.8 19.6 + 0.2
Baked sherry 17.4 17.6 -0.2
The aim was to develop a method for wine alcohol
having acceptable precision and accuracy and, equally
important, simple enough for less-experienced analysts
to conduct successfully. Most laboratory workers are
quite familiar with correct operation of the Cash still,
Standard and most winery laboratories have at least one avail-
deviation
able for its primary purpose of volatile acid analysis. In
practice, one technician can easily attend to 3-4 stills
0.087
installed side by side, meanwhile preparing samples to
0.051 be distilled and adjusting distillates to volume after
0.144 distillation. All of the usual precautions must be ob-
0.048 served to ensure acceptable alcohol recovery during the
distillation: tightly fitting still joints, moderate rate of
distillation, and distilling into a small amount of cold
water contained in a cold receiver. The 5-ml wine sam-
ple can be pipetted with greater accuracy, of course,
t h a n the 1-ml sample used with the micro-distillation
apparatus.
The spectrophotometric m e a s u r e m e n t of chromic
ion is recommended over dichromate titration with
ferrous a m m o n i u m sulfate. Many analysts have diffi-
culty with the end-point, and the titration requires
maintaining two more solutions for reductant and in-
dicator. Of course, the advantage of speed is achieved
p r i m a r i l y from using a modern spectrophotometer
equipped with a flow-through sampling cell. Obvi-

ously, a simpler instrument can be used, with manual
cell filling, although at the cost of time. In fact, the
instrument with flow-through sampling will rapidly
pay for itself from savings in time alone.
LITERATURE CITED
1. Amerine, M. A., and C. S. Ough. Wine and Must Analysis.
J. Wiley and Sons, New York. 121 p. (1974).
2. Caputi, Jr., A., M. Ueda, and T. Brown. Spectrophotometric de-
Am. J. Enol. Vitic., Vol. 30, No. 1, 1979
ALCOHOL DETERMINATION m 63
termination of ethanol in wine. Am. J. Enol. Vitic. 19:160-5 (1968).
3. Guymon, J. F., and E. A. Crowell. The chemical determination
of alcohol in wines and stillage by dichromate. J. Assoc. Off. Agric.
Chem. 42:393-8 (1959).
4. Morrison, R. L., and T. S. Edwards. Semi-automatic determina-
tion of ethanol in wine by the micro-dichromate method. Am. J. Enol.
Vitic. 14:185-93 (1963).
5. Zimmermann, H. W. Studies on the dichromate method of al-
cohol determination. Am. J. Enol. Vitic. 14:205-13 (1963).