J. Inst. Brew., May-June 1998, Vol. 104, pp.

123-126

COLLABORATIVE DETERMINATION OF THE PH OF BEER AND WORT

Submitted on behalf oi; the Institute or Brewing Analysis Committee (Chairman F. R. Sharpe) by H. R. Harrison

A method for the determination of pH in wort and beer has been tested for precision by the Analysis
Committee of the Institute of Brewing.
Over the pH range 3.94 to 5.04 it was judged that precision values were independent of the pH value
of the sample. Values for r95 and RgB were 0.025 and 0.129 respectively.

Key Words: pH, beer (analysis methodfor), collaborative test. TABLE I. Raw data
Laboratory
The Analysis Committee of the Institute of Brewing (IOB) number Beer I Beer 2 Beer 3
appointed the following sub-committee to determine the
1 4.36 4.36 3.90 3.91 5.01 5.02
precision of a method for the determination of pH of beer and 2 4.49 4.50 3.97 3.97 5.06 5.05
wort: A. P. Mundy (Chairman), G. K. Buckee, M. Fogg, H. R. 3 4.42 4.42 3.96 3.96 5.00 5.01
Harrison, R. Kennedy, J. Byrne. 4 4.53 4.52 4.00 3.99 5.00 5.02
5 4.46 4.45 3.96 3.95 5.06 5.06
6 4.11 ** 4.12" 3.59''• 3.58** 4.82 ** 4.82'*
Introduction 7 4.50 4.52 3.98 3.99 5.12 5.13
There is currently no method in the Institute of Brewing 8 4.44 4.44 3.97 3.97 5.06 5.06
9 4.44 4.41 3.94 3.92 5.01 4.99
Methods of Analysis for the determination of pH in wort and
10 4.49 4.49 3.96"'+ 4.00*+ 5.08 5.08
beer. The Analysis Committee undertook to prepare and
11 4.38 4.39 3.90 3.93 5.06 **+ 5.10'*+
collaboratively test a method for possible inclusion in the IOB
12 4.46 4.47 3.97 3.98 5.05 5.05
Methods of Analysis. During the preparation of the method the 13 4.37 4.36 3.91 3.90 5.02 5.02
Analysis Committee considered current practice and recom 14 4.46 4.46 3.98 3.98 5.09 5.09
mendations in published texts as listed in the Appendix, Section 15 4.41 4.42 3.91 3.90 5.04 5.04
12 (Bibliography). 16 4.40 4.41 3.90 3.92 5.02 5.04
The type of pH meter and electrode was not specified in the 17 4.38 4.38 3.90 3.91 5.01 5.02
method since it was recognised that a wide variety are available 18 4.34 4.35 3.83 3.84 5.01 5.01
in current use within the brewing industry. 19 4.43 4.44 3.98 3.97 5.02 5.02
20 4.46 4.45 3.97 3.97 5.05 5.05
In order to determine the possible effects on precision from
21 4.39 4.38 3.92 3.91 5.06 5.05
variations in the methodology used by participants during
22 4.42 4.42 3.96 3.96 5.05 5.05
testing a questionnaire was circulated with the samples. The 23 4.37 4.36 3.91 3.92 5.07 5.07
questionnaire covered possible variability due to electrode type, 24 4.45 4.46 3.96 3.96 5.07 5.07
meter display and temperature compensation, buffer prepara 25 4.42 4.40 3.95 3.94 5.04 5.03
tion, method of degassing the sample, and whether or not the 26 4.47 4.49 4.00 4.00 5.12 5.12
sample was stirred during analysis. 27 4.33 4.32 3.86 3.86 5.01 4.99
2S 4.45 4.45 3.98 3.97 5.06 5.06
29 4.31 4.31 3.80 3.81 4.95 4.95
30 4.40 4.41 3.93 3.93 5.06 5.06
Experimental
31 4.40 4.42 3.91 3.91 5.05 5.05
The organisation of the collaborative trial and the statistical
32 4.35 4.35 3.95 3.95 5.06 5.07
treatment of the data were carried out according to the pro 33 4.32'•*+ 4.37**+ 3.86 3.86 4.92 4.91
cedures given in the International Standard ISO 57251. A 34 4.42 4.41 3.97 3.97 5.09 5.09
uniform design was employed and two samples of beer and one 35 4.35 4.34 3.92 3.95 4.95 4.94
of a stabilised (pasteurised) wort were distributed to 46 labora 36 4.40 4.42 3.89 3.88 5.02 5.03
tories. Participants were requested to determine the pH of the 37 4.43 4.42 3.96 3.96 5.02 5.02
samples, in duplicate, following the method supplied. A copy of 38 4.43 4.43 4.02 4.02 5.08 5.08
the method is given in the Appendix. Forty-three laboratories, 39 4.43 4.44 3.97 3.96 5.06 5.05
40 4.44 4.43 3.98 3.96 5.05 5.02
including 12 overseas, submitted results.
41 4.42 4.42 3.92 3.90 4.97 4.98
42 4.42 4.43 3.94 3.94 5.05 5.04
43 4.44 4.45 3.94 3.94 5.07 5.07
Results and Discussion
Raw data are presented in Table I. Participants were asked to ** indicates outlier by Dixon's test
report results to three decimal places where possible, but since **+indicates outlier by Cochrarfs test (but data retained for precision
calculations)
the majority reported values only to two, all results are
*+indicates straggler by Cochran's test (but data retained for
presented in this format. The results which were reported to precision calculations)
three places have been rounded up where the last digit was 5-9,
and rounded down if 1-4.

Statistical results and R95 were 0.025 and 0.129 respectively. The precision values
Dixons test identified all results from Laboratory 6 as and a summary are given in Tables II and III.
outliers, and so these were omitted from the calculations of
repeatability and reproducibility1. Cochran's test on the dupli Questionnaire results
cate results identified two outliers, one on beer 1 and one on the The results from the questionnaire revealed that a variety of
wort, and one straggler, on beer 2. Since the absolute differ different makes and models of electrodes were used by partici
ences were still small, and occurred in three different labora pants in the collaborative test. Thirty-four used combination
tories, these results were all retained for the precision electrodes, of which 25 were glass, 2 solid state and 7 "other"
calculations. (one participant used the in-built SCABA electrode). Seven
It was judged that over the pH range 3.94 to 5.04, precision participants used separate reference and measuring electrodes,
values were independent of the pH of the sample. Values for r« all of which were glass. The remaining participants did not state
This document is provided compliments of the Institute of Brewing and Distilling
www.ibd.org.uk Copyright - Journal of the Institute of Brewing
124 COLLABORATIVE DETERMINATION OK THE pH OK BEER AM) WORT [J. Insl. Brew.

TABLE II. Precision values 3. References

Becrl Beer 2 Wort 3.1 International Standard, Water for Analytical Laboratory
n 42 42 42 Use, Specification and Test Methods, ISO 3696, I987(E).
Mean 4.42 3.94 5.04
roj 0.026 0.025 0.022 4. Definitions
R« 0.139 0.127 0.121
4.1 The pH of a solution is defined by the equation.

pH=-logan
where an is the activity of hydrogen ions in the solution.
TABLE III. Precision summary

pH of beer and won 5. Principle

Level 3.94 5.04
n 42
0.025
r»<
0.129
the electrode type used. Participants 2 and 24 used solid state
electrodes, participant 41 used the SCABA pH electrode and
participants 5,15,33,36,42 and 43 used separate reference and
measuring electrodes. The results from the above participants
do not show any significant bias from the results from
participants using combination electrodes.
All the meters used, with one exception (participant 29) had
a digital display. Most participants read the display to 2
decimal places, the rest to 3. Almost all (40) report results to 2
decimal places, and 2 participants stated that they usually
reported to 1 decimal place.
Automatic Temperature Compensation was used by most
participants (34). The majority of participants do not attem-
perate the sample to any particular temperature, but tend to
measure the sample at room temperature.
Thirty-five participants stated that they use ready prepared
buffers, 6 used tablets and 2 used ampoules which they then
diluted. Of the ones which used ready made buffers, most did
not check them for accuracy (although some came with
certificates from either the manufacturers or certifying body).
During the preparation of the sample, only one laboratory
did not usually degas. Of the others, 27 used filtration, 8
shaking, 3 ultrasonics, 1 pouring and 4 "other methods1', to
degas the sample.
Sixteen participants stirred the sample during measurement,
the rest did not.
S.I Because the hydrogen ion activities cannot be determined
experimentally, the pH of a solution is determined by
measuring the electromotive force (emf) of a cell containing the
test solution and comparing it with the emf of a similar cell in
which the test solution is replaced by a standard buffer
solution. The potential difference E generated between the pair
of electrodes which constitute the cell is given by the Nernst
equation:
2.3026RT pH
E=Eo-
nF
where Eo is a constant, R is the gas constant, F is the Faraday
constant, T is the temperature in Kelvin and n is the ionic
charge (1 for hydrogen ions).
5.2 The pH value is thus a pure number. The scale is anchored
by defining the nature of the standard solution and assigning a
pH value to it.
5.3 The slope factor 2.3026RT/F varies with temperature and
for this reason it is desirable that the buffer solution and the
samples are at the same temperature. Since pH changes with
temperature, the meter is calibrated to the pH of the buffer at
20°C and results are expressed at 20°C.
6. Reagents
Unless otherwise stated, use only reagents of recognised
analytical grade.
6.1 Water of at least Grade 3 as defined in ISO 3696-1987. For
the preparation of standard buffer solutions Grade 3 water
which has been freshly boiled must be used. Water used for the
preparation of buffer solutions must have a carbon dioxide
concentration no greater than that of air-equilibrated water.

6.2 Concentrated potassium chloride. The reference electrode

should be stored in concentrated potassium chloride solution
Conclusions
(e.g. 4M). This solution can be made up by adding approxi
The precision of the method was judged to be satisfactory
mately 75 ± 1 g of potassium chloride to 25O± I ml water and, if
and the method is recommended for inclusion in the IOB
necessary, gently warming to aid dissolution.
Methods of Analysis.
6.3 Buffer solutions

6.3.1 Buffer solutions have pH values which are well defined at

References
1. Precision of lest methods—Determination of repeatability and
specific temperatures and insensitive to small additions of acid
rcproducibility Tor a standard test method by inter-laboratory or alkali. A range of buffer solutions of accurately known pH
tests. ISO 5725. 1986. can be prepared in accordance with BS 1647: Part 2 which
should be consulted for full details. Alternatively commercial
buffer solutions or tablets for their preparation can be
APPENDIX purchased. The buffer solutions used should ideally cover the
PH OF BEER AND WORT expected range of pH results for the samples to be tested.
Warning and Safety Precautions Although buffer solutions are considered to be stable, it is good
practice not to use buffer solutions which are more one month
Refer to Section 0. old, and to discard them after a single use.
1. Scope 6.3.2 For the pH of beer and wort, a two point calibration
The determination of pH at 20°C of beer and wort using a pH using buffers of pH 4.00 and pH 7.00*0.02 is acceptable.
meter and a suitable electrode system. Ideally the expected measurement range should not exceed the
calibration range of the buffers.
2. Field or Application 6.3.3. For notes on preparation of primary pH standards see
The method can be applied to all beers and worts. 11.2 and 11.3.
This document is provided compliments of the Institute of Brewing and Distilling
www.ibd.org.uk Copyright - Journal of the Institute of Brewing
 Vol. 104, 1998] COLLABORATIVE DETERMINATION OF THE I'll OK BEER AND WORT
7. Apparatus
7.1 pH meter. This is a high impedance voltmeter (typically
greater than 10" ohms) designed to measure the potential
difference developed between the glass electrode and the
reference electrode, calibrated directly in pH and reading to
0.01 pH or better.
7.2 Electrodes
7.2.1 Glass pH and calomel reference electrode, or suitable
combination electrode, including solid state electrodes. It
should be noted that certain types of glass electrode must be
used with the corresponding type of reference electrode. In
general, separate glass and reference electrodes are considered
more reliable than combination electrodes. Of the commonly
used reference electrodes, calomel electrodes are preferred to
silver-silver chloride electrodes because the liquid junction is
less prone to blocking. It is important to ensure that the level
of reference electrode filling solution is well maintained and
that there are no air bubbles in the solution.
7.2.2 Whatever electrode is chosen, performance not only
varies between different manufacturers' products but also
between batches of the same manufacturer's electrodes. Some
new electrodes drift initially and so therefore must be pre
conditioned according to the manufacturer's instructions.
7.2.3 For notes on checking electrode performance
section 11.
7.3 Thermometer capable of reading to 0.1 °C or temperature
probe to fit pH meter.
7.4 Sample beakers 100 ml or larger.
7.5 Magnetic stirrer and followers.
8. Sample Preparation
8.1 Check the temperature of the sample solution, and for
maximum accuracy ensure that it is within* 1°C of the buffer
temperatures, for example 20°C± 1°C.
8.2 Degas the sample solution if necessary to remove carbon
dioxide. This can be achieved by filtering through medium fast
qualitative filter paper.
9. Procedure
Calibration of the pH meter.
This should be carried out at least daily and preferably for
each batch of analyses. pH is quoted at 20°C but using auto
matic temperature compensation, measurement and calibration
can be carried out at other temperatures provided that both the
samples and buffers are measured at the same temperature
±1°C.
9.1 Switch on the pH meter if necessary and allow to stabilise.
To improve the stability, instruments may be left on per
manently.
9.2 Remove the electrodes from their respective storage
solution(s), rinse thoroughly with and immerse in, water.
9.3 Measure the temperature of the buffer solutions and set the
automatic temperature compensation (ATC). If ATC is not
present, then the buffers and samples must be attemperated to
2O±2°C. Calibration should always be performed with buffers
and samples at the same temperature (±1°C), even when
temperature compensation is used. This is because the tempera
ture compensator adjusts the readings for the slope at a given
temperature, but cannot take into account the change of slope
with temperature differences.
9.4 Wash the electrodes with, and immerse in, pH 7 buffer.
9.5 Swirl the solution, or stir using a magnetic stirrer or
follower. Allow the solution to come to rest.
This document is provided compliments of the Institute of Brewing and Distilling
www.ibd.org.uk
125
9.6 Set the instrument to read the pH of the buffer solution at
208C by adjustment of the appropriate controls (refer to
manufacturer's instructions). The reading should be recorded
when it becomes constant. Refer to buffer solution data for the
exact value of the buffer solution at 20°C.
9.7 Rinse the electrodes thoroughly with distilled water and
pH 4 buffer solution.
9.8 Immerse the electrodes in the pH 4 buffer solution and
check that the instrument records the correct pH reading for
20°C. If not, where available, adjust the slope control. The slope
should be 58.2+1 at 20°C for acceptable readings.
9.9 Rinse the electrodes thoroughly with water and pH 7 buffer
solution. Repeat steps 9.4 and 9.5. If the pH reading is not
7.00±0.02 the calibration should be repeated.
9.10 Rinse the electrodes with and immerse in water to remove
any traces of buffer. Discard buffer solutions after use.
pH measurement
9.11 Wash the electrodes thoroughly with sample solution.
9.12 Immerse the electrodes in the sample solution, stir or swirl
gently for approximately one minute, then stop stirring and
record the pH when it has stabilised. If the pH reading does not
stabilise it may be a function of the type of sample or may
see
indicate that the pH of the solution is changing. To minimise
stabilisation difficulties it is advisable to analyse samples of a
similar composition and/or pH range consecutively.
9.13 Store the electrodes in pH 4 buffer after use.
10. Expression oe Results
10.1 Report the pH result to 2 decimal places at 20°C. pH has
no units of measurement but is expressed at 20°C.
10.2 Precision.
The results of a recent collaborative study will be published in
1998.
11. Notes
11.1 The ideal slope factor at 20°C (293K) is 58.17 mV.
Measurement of the slope factor gives an indication of the
performance of the electrode system, and if the value drops to
below 57.17 at 20°C, the electrode system requires recondi
tioning or replacing. The variation of the slope factor with
temperature is shown in Table I.
TABLE I. Variation of Slope l-'actor with Temperature
Temperature °C 2.3026 RT/F, mV Acceptable Practical Range*. mV
0.00 54.20 53.20-55.20
5.00 55.19 54.19 56.19
10.00 56.18 55.18-57.18
15.00 57.17 56.17-58.17
20.00 58.17 57.17-59.17
25.00 59.16 58.16 60.16
30.00 60.15 59.15 61.15
*±2% of theoretical value
11.2 Preparation of pH 4.0 solution: primary standard. At
20°C dissolve 10.138:2:0.001 g of potassium hydrogen
phthalate, previously dried at 105°C and cooled and stored in a
desiccator, in about 500 ml of water and dilute with water to
1 litre in a volumetric flask. The pH of this solution at 20°C is
4.001.
11.3 Preparation of pH 6.88 solution: primary standard.
Dissolve 3.40 g of KH:PO4 and 3.55 g of Na^HPO, (dried for
2 hours at 110-l30°C) in carbon dioxide free water and dilute
to 1 litre. The pH of this solution at 20°C is 6.881.
Copyright - Journal of the Institute of Brewing
126 COLLABORATIVE DETERMINATION OF THE Pll OF BEER AND WORT [J. Inst. Brew.

11.4 Electrode maintenance. Proper electrode maintenance 12.2 Guide to pH measurement, Mettler Toledo.
ensures a Taster response, more reliable measurements and a 12.3 pH Theory and Practice, Radiometer Copenhagen.
longer lifetime. Dirty electrodes will give low results on beer
and wort, but normal results on buffer solutions. A regular 12.4 BS1647: Part 2 1984, British Standards Institution,
cleaning regime, following manufacturers' instructions for the London 1984.
type of electrode used is recommended. 12.5 The Determination of pH in Low Ionic Strength Waters
11.5 It is possible that the porous junction of the reference 1988, HMSO, London.
electrode may become clogged by complexes containing protein 12.6 Recommendations about Wort and Beer pH
and tannin material and for this reason large porous junctions
measurement, M. Benard and R. Scriban, Journal of the
are preferred. A protection device to overcome this has been
Institute of Brewing, (1980), 86,177.
suggested (see 12.6).

12. Bibliography

12.1 A Textbook of Quantitative Inorganic Analysis, 3rd

edition, 1961, A. Vogel.

This document is provided compliments of the Institute of Brewing and Distilling

www.ibd.org.uk Copyright - Journal of the Institute of Brewing