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14 November 1998

Procedure for Alcohol Determination by Distillation


1.0

Introduction

The following notes discuss the procedure for determination of the alcohol in beer based upon ASBC MOA
Beer 4A as implemented in our laboratory. Comments are also included on the expected recovery and accuracy of
determinations done in this way.

2.0

Method

The method consists of execution of the following enumerated steps. See Figure 1 for an illustration of the
configuration of the apparatus.
1.

Pour beer into 100 mL volumetric flask (use the one labeled 7 as its mark is high up
on the neck.) Use a 1 mL Tensette pipet to suck foam out of neck. Fill to the mark or
just above. Stopper and place in 20C water bath.

2.

While beer is attemperating pull microwave oven away from wall. Place jack stand on
top of microwave oven. Elevate so that top of platform is about 8 above top of microwave. Place 500 mL mantle on top of jack stand with control knob facing about 30 to
the right of forward.

3.

Place Cole-Parmer ringstand (with white base) to left of microwave oven. Base should
be behind rod and rod should carry two clamps oriented away form base i.e. towards
front of microwave.

4.

After beer has attemperated, suck out excess beer and foam so level is at the mark.

5.

Fill two 25 mL flasks with DI water to near the marks.

6.

Pour beer into 500 mL distillation flask. Rinse with two 25 mL portions of DI water.
Add a couple of carborundum boiling stones.

7.

Place distillation flask in mantle. Stabilize with clamp on mantle rod.

8.

Place Kjeldahl trap in flask neck. Stabilize with clamp on mantle rod.

9.

Connect bridge adapter to top of trap. Be sure thermometer port is plugged with glass
stopper.

10.

Rinse 100 mL volumetric flask with DI water and place in 500 mL beaker on counter
top.

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11.

Place straight adapter on end of 400 mm condenser and while holding it in place
lower its end into volumetric flask. Place condenser into two clamps on Cole Parmer
ringstand without tightening. Simultaneously lower jack and position receiver, ringstand and bridge adapter angle so that bridge adapter mates with top of condenser.
Adjust postitions so that all glass joints are tight and so that there is a little clearance
between the straight adapter and the mouth of the volumetric flask. Tighten the
clamps.

12.

Make and check the cooling water connections.

13.

Surround the receiver with ice cubes in a little water, turn on the cooling water and set
the mantle control to 10 for 10 minutes, then lower heat setting to 6. There should be
some reflux from the neck of the flask during this time.

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14.

Recheck tighness of all ground glass joints.

Figure 2.1

Arrangement of distillation apparatus

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15.

Boiling should commence within a minute or so and reflux from the walls of the
Kjeldahl adapter should start. If all goes well, the alcohol in this reflux should collapse
the foam. If it doesnt, well thats what the trap is there for.

16.

After 20 minutes (total) foaming should be under control and alcohol should be seen
dropping from condenser tip into straight adapter. Advance heat to 7. After stabilizing, condensate should appear at about 10 - 20 drops per minute.

17.

After 1 hour (total) raise heat to 8. Check tightness of glass joints.

18.

During distillation tare pycnometer, if pycnometer is being used, and obtain weight
measurement with DI water at 20C

19.

Collect just under 100 mL of distillate. This should take about 2 and three quarters
hours.

20.

Place volumetric flask in water bath. After attemperation, make to mark with DI
water. Mix throroughly. Measure and record density, specific gravity and OIML ABV.
Find ASBC ABV from ASBC tables. Calculate ABW from grams/100 mL in ASBC
tables.

21.

Transfer residue from distillation flask to same volumetric flask. Rinse distillation
flask with 25 mL portions of DI water. Place in water bath and make to mark with DI
water. Measure and record density, specific gravity and P.

22.

Measure and record specific gravity, density and P of beer.

23.

Do the sums!

3.0

Accuracy
There are five factors which effect the acheivable accuracy

Measurement

Conversion

Recovery

The standard

Interferences

The alcohol content in the distillate is estimated by measuring the distillate specific gravity (or density) and then converting this reading to an alcohol concentration by entering a table. Error in measurement of specific gravity thus
translates into an error in the reported alcohol content we take out of the table. The table itself has some errors in it as
it was at some time based on a set of measurements. It is clear that the ASBC table, at least, contains quantizing
errors.

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Recovery refers to the fact that in this method we try to remove the alcohol from the beer sample in order
to measure it. We cannot recover all the alcohol in the distillation receiver. That which is not recovered is not counted.
If we can obtain an estimate of the fraction of the alcohol not recovered we can adjust the amount determined by specific gravity measurement in order to account for it. Our estimate of the recovery is subject to error and depends upon
our knowledge of the purity of the standard used in making the estimate.
Intereference refers to other substances in the beer which interfere with our ability to measure ethanol. Substances more volatile than alcohol and substances less volatile than alcohol but more volatile than water will be carried over into the distillate in some measure. We assume, for this work, that the amounts of such volatile substances
are small enough that they need not be considered. DeClerk focuses on acetic acid noting that it is present in quantities insufficient to make much of a difference except in the case of lambics. He notes (Vol. II p429) that raising the pH
of the beer with alkali dissociates the acid and prevents its being volatilized but that this leads to frothing and inability
to determine the true extract. We will say no more about interference.

3.1

Measurement

Two types of measurements are made when beer alcohol is determined using this methodology. The first
tyhpe of measurement is of the volumes of beer and distillate. The second is in the specific gravity of the distillate.

3.2

Volume Measurement

Volumes are measured with the same Class A 100 mL volumetric flask specified as 100 0.08 mL. If this
value (0.08) is interpreted as being the standard deviation of the random error in filling the flask it is clear that the
alcohol determined should be multiplied by the factor
100 +
f = -------------------d100 + b

(3.1)

where b represents the error in filling the flask with beer (to include the error in transfer to the distilling flask) and
d the error in topping off the distillate with deionized water. Though common sense dictates that the standard devitation associated with b should be larger than that associated with d because of the transfer of beer to the distilling
flask we have no feel for how much larger and thus, to keep the analysis simple, make no adjustment for this. Expanding Equation (3.1) and throwing away second order terms gives
d
b
- + -------f = 1 -------100 100

(3.2)

2 b
from which we see that the expected value of f is one and the standard deviation in f is ------------- where b is the stan100
dard deviation associated with filling the flask (0.08 mL) and thus the standard deviation in f is 0.00113. Thus, at the
10% level the error budgeted to this source would be 0.0113%.

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3.3

Specific Gravity Measurement

To determine alcohol content we measure the density of distillate from the beer sample which distillate is
assumed to contain all the alcohol in the sample and nothing else except water. We use an Anton Paar DMA 5000
Density Meter calibrated against dry air and deionized, degassed water. The specified repeatability for this instrument
is 0.000001 and its accuracy is specified as 0.000005 grams/cm3. The error in specific gravity measurement is seen
through its conversion to an error in alcohol content (see section which follows). Figure 3.2 shows the sensitivity
(partial differential of) ABV to specific gravity taken from the ASBC (based on table Association of Official Agricultural Chemists) tables. For example, at an ABV of 5% Figure 3.2 shows a sensitivity of -740% ABV for each unit of
error in specific gravity. The repeatability of alcohol concentration estimates for solutions near 5% is thus 0.000740%
and the overal accuracy 0.0037%1. At 9.5% ABV the uncertainty in alcohol content from a specific gravity uncertainty of 0.000005 is 0.0042% and it is this value that we will budget for the error contribution from density measurement.

3.4

Conversion

The measured specific gravity is enterend into the ASBC table (based on table Association of Official Agricultural Chemists) and the alcohol content taken out.The data from this table is plotted in Figure 3.1. In fact we use an
Anton Paar DMA5000 density meter which measures the density of the alcohol solution and looks up the ABV value
using tables prepared by the OIML (International Organisation of Legal Metrology) rather than the ASBC tables2.
The two tables are presumed close. We checked at specific gravity 0.98650. According to the ASBC tables the ABV
for solutions at this specific gravity is 10.000%. Examination of ABVs determined by the DMA 5000 indicate that
the OIML value for this same specific gravity is 9.984% or 0.016% lower than the ASBC tables reading.
Chi squared in fitting the ASBC data is given on Figure 3.1 as 0.01455 for 501 points corresponding to an
rmse of 0.0054%. The OIML tables are not accesible. We assume that they are about the same and we thus budget
0.0054% for conversion error.

1.

Given that the instrument deviations are interpreted as standard deviations then these error values are standard deviations as well. The values should be increased sligtly (1/0.998203 i.e. about
0.2% - i.e. percent of a percent) because the instrument spec values are for density, not specific gravvity.
2. We

note that the DMA 5000 does contain the AOAC tables but as the instrument was programmed for the OIML method as it came from the factory we have stayed with it. Note further
that the OIML tables are based on ITS90 and, therefor, presumably more accurate than the AOAC
tables which were published originally in 1930.

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x10

-3

10

-10
10
9

ABV vs. Specific Gravity


Fit to ASBC Tables
W_coef={1.7417e+05,-5.1755e+05,
5.1323e+05,-1.6986e+05}
V_chisq= 0.0145526; V_npnts= 501;
W_sigma={5.06e+03,1.53e+04,
1.54e+04,5.17e+03}

8
7

ABV, %

6
5
4
3
2
1
0

Alcohol: ABV vs SG

0.988

0.990

0.992

0.994

0.996

0.998

1.000

Specific gravity (20C/20C)

Figure 3.1

3.5

Polynomial Fit to ASBC (AOAC) Alcohol Table

Recovery

To check on recovery we made up 1 L of an approximately 10% v/v solution of EtOH and measured the
alcohol content of 7 aliquots using the method described here. Class A glassware was used to measure out 100 mL of
ethanol and DI water was added to make up to 1000 mL. Alcohol and water measurements were made with volumetric flasks in a constant temperature bath at 20C. The 100 mL volumetric flask used to measure the alcohol is rated
0.08 mL and the 1 litre volumetric flask used to make up with water is rated 0.3 mL. We interpret these numbers as
standard deviations. The strength of the solution by volume is,
( p + p ) ( V a + a )
A = -----------------------------------------V s + s

(3.3)

where p is the purity of the ethanol standard (fraction close to 1), p is the uncertainty in the purity, V a is the vol-

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-680

ABV Error From S.G. Uncertainty


To Estimate ABV Error Multiply
Value Read From Graph Against
Alcohol Content By SEM in SG
Reading

ABV/ Specific Gravity, %

-700
-720
-740
-760
-780
-800
-820
-840
Alcohol:dabvdsg vs ABV

10

ABV, %

Figure 3.2

ABV Error Sensitivity to Error in Density vs ABV

ume (100 mL in this case ) of alcohol transferred quantitatively to the V s (1 L) volumetric flask and a and s represent the standard errors in the volumes of the two volumetric flasks.
Rearranging Equation (3.3)
pV a + p a + p V a + p a s pV a + p s a + s p V a + p a s
A = ----------------------------------------------------------- ------------------------------------------------------------------------------Vs
V s2

(3.4)

Separating the actual strength from the errors we have


pV
p p V a s pV a
A = ---------a- + -------a- + ----------- -------------Vs
Vs
Vs
V s2

(3.5)

where we have dropped all second order and higher terms.in the uncertainties and, thus, assuming that the three

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uncertainties are small and independent we find


Va
EA = ----------1000

(3.6)

( p a ) 2 + ( p V a ) 2 + ( s pV a 1000 ) 2
.
A = -----------------------------------------------------------------------------------------1000

(3.7)

Both these values are fractional values. If V a is 100 mL then the expected strength of the solution is 10% and the
standard error is 0.0086%. The accuracy of the 100 mL volumetric flask is the major contributor. Were it the only
source of error the uncertainty in the concentration would be 0.0080%. The second largest contributor is the uncertainty in the volume of the 1L volumetric flask. Were this the only error source the uncertainty would be 0.003%.
The ethanol used to prepare this solution is not 100% pure. It is guaranteed by the label to have a minimum
assay of 99.5%. We assayed it by measuring its density at 20C. The measurement ensemble is given in the upper left
portion of Figure 3.3. Two of the readings in this set appear to contain errors three times that of the rest of the group.
These are discarded in the upper right grouping of measuremets which give an ensemble average of is 99.876% with
an SEM of 0.00006%. This uncertainty is clearly dominated by the uncertainty from the volume measurements if the
two errors are RSSd. Thus we consider a solution prepared from 100 mL of this ethanol to be 9.9876 0.0086% ethanol.
Measured values from the individual distillation runs are compared to 9.9876% in the spreadsheet and the
average readings used to determine the recovery for our lab. Thus the uncertainty in the strength of the standard
becomes and uncertainty in every measurement of a sample which is adjusted by the average recovery determined by
these calibration runs. At the 10% level this uncertainty would be 0.0086% and it is that value which is budgeted..

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Alcohol Assay
ABV
Density
ABV dev
Dens Dev
99.915
0.78968
0.084
-0.00043
99.917
0.789672
0.086
-0.00044
99.884
0.78984
0.053
-0.00027
99.884
0.789843
0.053
-0.00027
99.87
0.789912
0.039
-0.00020
99.876
0.789885
0.045
-0.00023
99.687
0.790852
-0.144
0.00074
99.614
99.827
99.835
99.8309
0.101
0.032

0.791224
0.790138
0.790094

1
2
3
4
5
6
7
u
sd
cv

0.00111
0.00002
-0.00002

0.790114 u
0.000517 sd
0.000163 sem

Solution (100 mL in 1L):


Replicate

-0.217
-0.004
0.004

Alcohol Assay
ABV
Density
ABV dev
Dens Dev
99.915
0.78968
0.084
-0.00043
99.917
0.789672
0.086
-0.00044
99.884
0.78984
0.053
-0.00027
99.884
0.789843
0.053
-0.00027
99.87
0.789912
0.039
-0.00020
99.876
0.789885
0.045
-0.00023
99.827
0.790138
-0.004
0.00002
0.790094

0.004

99.876
0.033
0.012

0.789883 u
0.000169 sd
0.000060 sem

-0.00002

9.9876 %

Distil. Assay Recovery


Err
9.871
98.83%
9.9193
99.32%
9.9192
99.32%
9.9295
99.42%
9.9338
99.46%
9.9309
99.43%
9.9416
99.54%
9.92075714
0.02332444
0.24%

Figure 3.3

99.835

-0.1166
-0.0683
-0.0684
-0.0581
-0.0538
-0.0567
-0.046

99.33% RMSE:
0.23%

Err^2
0.01359556
0.00466489
0.00467856
0.00337561
0.00289444
0.00321489
0.002116

Adjby Rec.
9.93750761
9.98613304
9.98603237
9.99640176
10.0007307
9.9978112
10.0085833

0.07024442

Err
-0.0500924
-0.001467
-0.0015676
0.00880176
0.01313074
0.0102112
0.02098329
RMSE:

Err^2
0.00250925
2.152E-06
2.4575E-06
7.7471E-05
0.00017242
0.00010427
0.0004403
0.02173973

OIML Measurements of Alcohol Standard and


Recovery from Solution of 100 mL Standard in 1000 mL
DI Water

Thus we model the recovery as 99.33 0.23% i.e. it represents a bias plus a random component. As we did
in the tests with standard solutions we would multiply all determined values by the factor 1.0067 (the reciprocal of
0.9923) to account for the alcohol held up in the distillation apparatus and lost to evaporation. This value is relevent
only to our laboratory and our implementation of the procedure. At the same time we add the random part of the
determined recovery to our error budget. At an alcohol content of 10% this would be 0.023%

3.6

Summary of Errors

The table which follows summarizes the error sources. The RSS of all of them is about 0.03% and that is the
estimate of the error level of which we think we are capable in the absence of interferences.

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Table 1:
Error Source

4.0

RMSE

Volume Measurement

0.0113%

Specific Gravity Measurement

0.0042%

Tabulation Error

0.0054%

Recovery

0.023%

Calibration Standard

0.0086%

RSS

0.0278%

References
1.

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