19.

Determination of the alcohol content in beverages – distillation method

Accurate alcoholic beverages analysis ensures excellent beverages quality [1]. Therefore this analysis
is an essential part of the daily work in the labs in the breweries, vineyards and distilleries.
Knowledge of the alcohol content is necessary to ensure that the beverage conforms to the label
declaration of alcohol content [2] and to establish the basis for the payment of tax [3].
Distillation. Distillation is the most important method of separation and purification of liquids. In the
simplest case of distillation liquid is heated to boiling and produced vapor is condensed in a
condenser and collected as a distillate. Distillation when only one phase is in the motion – vapor – is
called simple distillation. Distillation when portion of condensed vapor still flow down into the
distillation flask is called rectification. Rectification is performed using fractionating column [4].
Many substances form azeotrope mixtures, which at definite composition show maximal or minimal
boiling temperature. Azeotrope mixture cannot be separated by distillation because vapor and liquid
phase have the same composition. The example of azeotrope mixture is exactly water-ethanol
mixture. The mixture containing 95 % by mass of ethanol boils at the lower temperature i.e. 78,15 °C,
than pure water (100 °C) or pure ethanol (78,3 °C).
The following diagram shows the phase equilibrium between liquid and vapor in the function of
concentration for water-ethanol mixtures [5].

Suppose, we are going to distill a mixture of water and ethanol with composition C1. It will boil at a
temperature given by a liquid curve and produce a vapor with composition C2. When a vapor
condenses it will still have the composition C2. If we reboil this new mixture it will produce a new
vapor with composition C3. If we carried on with this boiling-condensing-reboiling procedure we end
up with a vapor with a composition of 95 % by mass of ethanol. If we condense this vapor we gat a
liquid with this same composition. Because of liquid and vapor curves meet at this point, each time
when we boil the liquid with the composition of 95 % by mass of ethanol, the condensed vapor still
has the same composition of 95 % by mass of ethanol. It means that it is impossible to get pure
ethanol (100 %) by distilling any mixture of water-ethanol containing less than 95 % by mass of
ethanol. This particular mixture of ethanol and water boils as if it were a pure liquid. It has a
constant boiling point and the vapor composition is exactly the same as the liquid. This liquid is
known as an azeotrope.
In the consequences of this for fractional distillation of dilute aqueous solutions of ethanol we cannot
get pure ethanol, but only a product with a maximum concentration of 95 % of ethanol. What we can
get it is a pure water, of course if we earlier ethanol rich vapor given off from the distillation flask.

© Faculty of Chemistry, University of Wrocław, Analytical Chemistry Dept., distillation. Task 19 - p. 1

Pure ethanol can be produce only by the fractional distillation of ethanol-water mixtures containing
more than 95 % by mass of ethanol. In this case we get a distillate containing 95 % of ethanol in the
collecting flask and pure ethanol in the boiling flask.

Determination of alcohol content in beverages – distillation method. The base of the method of the
determination of alcohol content in beverages is a precise measurement of volume (or weight) of a
degassed and filtered sample of beverage. The sample is quantitatively transferred to the distillation
apparatus, then the distillation is performed and the obtained alcohol fraction is filled up to the
original volume (or weight) with distilled water. In this way a liquid is obtained which has the same
alcohol concentration as the original sample but no longer has extract. The alcohol concentration in
% by vol. or in % by mass is determined highly accurately via density or refractive index
measurements and an appropriate alcohol concentration tables [6-11].
The alcoholic strength by volume is the number of liters of ethanol contained in 100 liters of
beverage, both volumes being measured at a temperature of 20 °C. It is expressed by the symbol '%
by vol'.
Homologues of ethanol, together with the ethanol and ethanol homologues in ethyl esters, are
included in the alcoholic strength since they occur in the distillate.

Methods of measurements of alcohol content in distillate. The alcohol content in a distillate can be
determined using [8, 9, 12]:
pycnometer – determination of density or specific gravity of distillate – method basing on a
precise measurement of a mass of liquid,
areometer (hydrometer), alcoholometer – determination of density, specific gravity or alcohol
concentration of distillate – method basing on buoyancy,
hydrostatic weighing – determination of density of distillate – method basing on buoyancy,
digital density meter – determination of density of distillate – measurements of the frequency of
oscillation of the U-shaped tube filled with a sample,
refractometer – measurement of the refractive index of a distillate,
spectrometer – measurement of the alcohol-specific range of the near infrared (NIR) spectrum.

Aim of exercise The aim of this activity is a distillation of a sample of a chosen beverage like beer,
wine, sparkling wine, liqueur, tincture or mead and determination of alcohol content in received
distillate.

Materials:
- round flat-bottomed flask with ground - Pasteur pipette with nipple,
glass joint per 1000 cm3, - funnel,
- 2 round flat-bottomed flasks with - cellulose wool or filter paper,
ground glass joint per 500 cm3, - analytical balance Radwag WPS 600/C,
- Erlenmeyer flask with ground glass joint - graduated cylinder per 250 cm3,
per 250 cm3, - graduated cylinder per 25 cm3,
- Liebig condenser, - hydrometer calibrated from 0,900 to
- fractionating column, 1,000 g/cm3,
- thermometer with ground glass joint, - thermometer,
- rubber tubing, - magnifying glass.
- heating mantle,
- laboratory support jack, Chemicals:
- laboratory stand, - 2 M suspension of Ca(OH)2,
- condenser clamp + clamps holder, - distilled water,
- glass beads or pumice pieces, - indicator paper.

© Faculty of Chemistry, University of Wrocław, Analytical Chemistry Dept., distillation. Task 19 - p. 2

PROCEDURE
Sample preparation. If the analyzed sample is a beer or a sparkling wine – the sample should be
degassed. In this purpose pour about 350 cm3 of the sample to round flat-bottomed flask per 1000
cm3 and stir it as long as the pressure of carbon dioxide in the flask is detectable by hand. Next filter
the sample through the cellulose wool or filter paper to a round flat-bottomed flask per 500 cm3.

Analysis. Weigh precisely 200 ±0,1 g of prepared sample in a clean and dry tared round flat-
bottomed flask per 500 cm3 on a balance (last drops of a sample should be added carefully with a
Pasteur pipette). Next add about 30 cm3 of distilled water. If the analyzed sample is a wine or a
mead add additionally 10 cm3 of 2 M Ca(OH)2 in the presence of an indicator paper to neutralize the
solution. Next add a few glass beads or pumice pieces.
Place the flask in the heating mantle and join it with a fractionating column and the Liebig
condenser and tared Erlenmeyer flask with ground glass joint per 250 cm3 (the mass of the clean,
dry and empty!!! Erlenmeyer flask note down earlier in the lab-book). Join the rubber tubing with

© Faculty of Chemistry, University of Wrocław, Analytical Chemistry Dept., distillation. Task 19 - p. 3

the condenser – cooling water should enter through the lower fitting and exit through the upper
fitting. Ask the assistant to check the correctness of the connections of apparatus.
Turn on the cooling water flow and begin heating the flask with a mantle. Adjust heat as necessary
to achieve uniformly boiling of the liquid. Distill as long as you receive in the collecting flask about
180 cm3 of a liquid. End up the distillation process – disconnect the electric power, turn off the
water, cool down the apparatus and disconnect the condenser.
Place the collecting flask with the distillate in the analytical balance and fill up drop by drop with
distilled water to 200,0 g of the liquid with ±0,1 g accuracy. Plug the flask and gently swirl the liquid.
Measurements of the distillate density, ρsample .
t C

a) Hydrometry. Pour the distillate into the measuring cylinder per 250 cm3. Ensure that the cylinder
is kept vertical. Insert carefully the thermometer and hydrometer. Read the temperature on the
thermometer two minutes after stirring to equilibrate the temperature of the measuring cylinder,
the thermometer, the hydrometer and the distillate. Write down the temperature in the lab-book.
Remove the thermometer and read the apparent density after one minute. Take at least three
readings using a magnifying glass and write down the measured density ρsample
t C
in the lab-book.
Calculations. In order to determine the alcohol strength expressed in % by mass refer to the
international alcoholometric tables [13]. Find in the tables the smallest density greater than the
measured density of sample, ρsample
t C
at the temperature t °C.
Alcohol strength expressed as % by vol. in the analyzed sample can be calculated from the following
formulae:
ρsample
t C

% by vol. % by mass
ρCH
t C
3CH 2 OH

where:
% by mass – is the ethanol strength by mass, ρCH
t C
3CH 2 OH
– is the density of ethanol at t °C, it can be
found in respective tables.
b) Densimetry using an automatic density meter Rudolph Research Analytical DDM 2911. Transfer
about 3 cm3 of the distillate to a clean and dry test-tube and cork it. To perform a measurement
please contact with doctor Andrzej Burakowski. Office 401A, phone number 375 7235. The
measurement could be performed during lab or in the other appointed time. Obtained data has to
be included in the final report.
Report
The report should be composed of:
 first name and last name of the person conducting the analysis,
 analysis’ date,
 all the necessary information enable to sample identification,
 short description of sample preparation and analysis,
 analysis’ result (if possible, comparison of the analysis’ result and the alcohol content
provided by the producer from the beverage’s label),
 comments.

BIBLIOGRAPHY
1. Anton Paar, Beer analysis using the Anton Paar Alcolyzer Plus beer analyzing system, Application Note.
2. Rozporządzenie Ministra Rolnictwa i Rozwoju Wsi z dnia 10 lipca 2007 r. w sprawie znakowania środków
spożywczych, Dziennik Ustaw 2007 nr 137 poz. 966.

© Faculty of Chemistry, University of Wrocław, Analytical Chemistry Dept., distillation. Task 19 - p. 4

3. Ustawa z dnia 6 grudnia 2008 r. o podatku akcyzowym, Dziennik Ustaw 2009 nr 3 poz. 11.
4. Preparatyka organiczna, Bolesław Bochwic (red.), Paostwowe Wydawnictwo Naukowe PWN, Warszawa
1971.
5. Jim Clark, Non-ideal mixtures of liquids, [Link]
6. Polish Norm PN-A-79093-2:2000 Beer – Testing methods – Determination of alcohol, real extract and basic
wort extract content by destilation and by refractometer method.
7. Polish Norm PN-A-79120-04:1990 Wines and meads. Preparation of samples and testing methods.
Determination of ethanol content.
8. The Commission Of The European Communities, Commission Regulation (EEC) No 2676/90 of 17
September 1990 determining Community methods for the analysis of wines, Official Journal of the
European Communities L 272 , 03/10/1990 P. 0001-0192.
9. International Organisation of Vine and Wine (OIV), Compendium of International Methods of Analysis of
Wines and Musts Vol. 1 & 2, OIV-MA-INT-00-2012 , Paris 2012.
10. International Organisation of Vine and Wine (OIV), Compendium of International Methods of Analysis of
Spirited Beverages, Alcohol and Beverage Aromatic Fraction, (Recueil des méthodes internationales
d’analyse des boissons spiritueuses des alcools et de la fraction aromatique des boissons, in French) Paris
1994.
11. International Union of Pure and Applied Chemistry, Applied Chemistry Division: Fermentation Industries
Section, A standardization of methods for determination of the alcohol content of beverages and distilled
potable spirits, Pure and Applied Chemistry 17 (1968) 273-312.
12. International Organization of Legal Metrology, International Recommendation OIML R 44 Edition 1985 (E),
Alcoholometers and alcohol hydrometers and thermometers for use in alcoholometry.
13. International alcoholometric tables, International Organization of Legal Metrology (OILM - Organisation
Internationale de Métrologie Légale) [Link]

© Faculty of Chemistry, University of Wrocław, Analytical Chemistry Dept., distillation. Task 19 - p. 5