Wine Pac: Wine P A C

Wine Potentiometric Analysis Collection
WINE PAC
6.6043.003
Methods for the titrimetric / potentiometric analysis

of wine
[
Dear Users,
You have purchased a Metrohm titrator which, with its collection of methods, is specially cus-
tom-made to meet your particular requirements. Metrohm always tries to provide the customer
with as wide a range of application support as possible so that the day-to-day analytical work
is made easier.
In the Application File you will find the descriptions of the corresponding analytical methods,
together with all the necessary remarks and explanations and – very important for you – print-
outs of the instrument parameters and examples of curves.
All these methods are loaded on the Method Memory Card. You only need to «feed» the titrator
with the card, load the required method into the working memory and off you go!!!
You are the specialists in wine production and have to ensure the outstanding quality of this
wonderful drink when it is sold to your customers. Although we at Metrohm do not understand
much about your profession, we have been ion analysis specialists for many years. The combi-
nation of these two elements – and we are convinced of this – will produce optimal results.
For Titrando users: A conversion program ensures that you can adopt the Titrino parameters
in your Titrando without any problems. This conversion program is contained in the PC Control
program.
We wish you pleasure and success in your work,
Your Metrohm
8.110.1793
1
A few additional hints
The methods presented here have been drawn up by taking the relevant methods of the individual coun-
tries into consideration (see literature references). These are methods from the EU, Australia, Israel, Switzer-
land, South Africa, South America and the USA.
All methods have been worked out so that you can use them as so-called SOPs (Standard Operating Pro-
cedures) in your laboratory.
Of course, almost all these methods can be further automated. In the appendix you will find a relevant exam-
ple. For details please contact your local Metrohm distributor, who can also be found on the Internet under:
www.metrohm.com Distributors
The supplied method memory card can be used with the following Titrinos: 798, 799, 785 and 751 (from
program version 20). With VESUV 3.0 Light, which is also supplied (VESUV = Verification Support for Valida-
tion), either you or your Metrohm agency can also transfer the parameter sets to the following Titrinos: 716,
736, 794 or 751 (<program version 20).
Among other things, the supplied CDs contain:
• The VESUV backup file, which allows you to copy the 25 methods into the 716, 736, 751, 785, 794, 798
and 799 Titrinos. For further information please read the Section «Recreating methods» in the VESUV In-
structions for Use, which is also supplied, or contact your local Metrohm agency. If, instead of the printer,
the VESUV software is used for adopting the data, then the «curve» report must be deleted at the Titrino,
which must be set to «mplist» instead (VESUV can only process measuring point lists).
• A conversion program (converter) for adopting the Titrino parameters in the Titrando is contained in the
6.6050.000 PC Control program.
• Acrobat Reader to be installed on your PC so that you can read PDF files.
• Application Bulletins No. 82, 83, 125, 129, 130, 133, 140 and 225.
We recommend that you only load the methods that you require into your instrument.
The method overview can be removed and stored together with the Wine PAC card and the appropriate
instrument.
Important symbols used in the methods

c(X) molar concentration of substance X in mol/L
M(X) molar mass of substance X in g/mol
w(X) mass fraction of substance X, e.g. w(ethanol) = 13.5%
ρ(X) mass concentration of substance X, e.g. ρ(NaCl) = 10 g/L
Abbreviations of countries
Au Australia and New Zealand
CH Switzerland
EU European Union
Israel
RSA South Africa
SA South America (Chile)
USA United States of America
2
Overview of chapters
A pH value
A1 Calibration of the measuring electrode
A2 pH measurement
B Total titratable acidity
B1 Preparation and titer determination of the titrant
B2 Titration procedures
C Free sulfurous acid (Free SO2)
C1 Preparation and titer determination of the titrant
C2 Orienting Ripper method (CH, SA, USA)
C3 Official reference method (Au, EU, Israel, RSA)
D Total sulfurous acid (Total SO2)
D1 Orienting Ripper method (SA, USA)
D2 Official reference method (Au, CH, EU, Israel, RSA, SA)
E Volatile acids
F Fixed acidity
G Ascorbic acid (vitamin C)
H Reducing sugars
H1 Preparing the solutions and determining the calibration factors
H2 Determining the content of reducing sugars
J Carbon dioxide (CO2)
K Ash and ash alkalinity
L Calcium and magnesium
M Chloride
N Total phosphorus
O Sulfate
P Direct potentiometric measurements with ion selective electrodes (ISE)
P1 Ammonium
P2 Potassium
P3 Sodium
P4 Fluoride
P5 Alcohol content with the fluoride ISE
3
Literature references
– Metrohm Application Bulletins nos. 82, 83, 125, 129, 130, 133, 140, 225
– Metrohm Ti Application Notes nos. T-30, T-72
– OIV Methods: Office International de la Vigne et du Vin, 11 rue Roquépine, F-75008 Paris (1992)
– C.S. Ough, M.A. Amerine
Methods for analysis of musts and wines, 2nd edition
John Wiley & Sons, New York 1988 ISBN 0-471-62757-7
– P. Iland, A. Ewart, J. Sitters, A. Markides, N. Bruer
Techniques for chemical analysis and quality control during winemaking (2000)
Patrick Iland Wine Promotion, Campbelltown, South Australia 5074
ISBN 0646-38435-X
– Edmundo Bordeu S., Juan Scarpa B-B.
Análisis químico del vino
Ediciones Universidad Católica de Chile (1998)
ISBN 956-14-0516-4
– Vorschriften zur Weinanalytik. Bundesamt für Weinbau, Eisenstadt (Austria)
– Jornal Oficial das Comunidades Europeias, Portugal
– Gazzetta Ufficiale della Repubblica Italiana, 2a Serie speciale N. 90 (1990)
– The Israeli Standard for Wine Determination, No. 1318
– Schweizerisches Lebensmittelbuch, Kapitel 30 + 30A, Wein aus Trauben
– Jakob, L.
Taschenbuch der Kellerwirtschaft
Fachverlag Dr. Fraund GmbH, Wiesbaden (Germany) 1984
– West, S.J., Frant, M.S., Anderson, M.G., Chandler, L.L.
A simple, accurate method for determining alcohol in wine using a fluoride ion-selective electrode
Thermo Orion (1999)
4
Method 1 –
A 1 Calibrating the measuring electrode
Recommended • 6.0258.000 Unitrode (comb. pH glass electrode with built-in Pt 1000 tem-
accessories perature sensor)
• Alternatively: 6.0259.100 Unitrode (comb. pH glass electrode) with 6.2104.020
electrode cable and separate thermometer
Reagents • Metrohm buffer solution pH = 4.00 (6.2307.100)

• Metrohm buffer solution pH = 7.00 (6.2307.110)
• DIN buffer solution pH = 6.865 at 25 °C (6.881 at 20 °C). 0.025 mol/L each of
KH2PO4 and Na2HPO4, e.g. Fluka no. 82557 or Merck no. 107202
Allgemeines • Buffer solution pH = 3.556 at 25 °C (3.57 at 20 °C). Saturated solution of
potassium hydrogen tartrate in dist. H2O. This solution is not commercially
available. 1...2 g KHC4H4O6 and approx. 0.1 g thymol are placed in a 200 mL
volumetric flask and dissolved in approx. 150 mL dist. H 2O under gentle heat-
ing to approx. 40...50 °C. After cooling down the solution is made up to the
mark with dist. H2O and mixed. This (preserved) buffer solution has a shelf
life of approx. 2 months.
A pH value
General The pH value is defined as the negative logarithm of the concentration of free,
dissociated hydrogen ions in mol/L: pH = –log[H+]
The pH scale ranges from 0 to.14 and the neutral point is at pH = 7.0, where H+-
und OH – ions are present in equilibrium. pH values <7 result from an excess of
H+, pH values >7 from an excess of OH –. The more acidic a solution, the lower
its pH; the more alkaline a solution, the higher its pH.
Weak acids, e.g. tartaric acid, do not dissociate completely, i.e. only a small
fraction (2...3%) of the H+ ions are released:
This also means that only on very rare occasions can the concentration of acids
or alkalis be inferred from the pH value.
As the pH scale is logarithmic, this also means that small differences in pH cor-
respond to large differences in the H+ concentrations. For example, at pH = 3.0
there are ten times as many H+ ions present than at pH = 4.0, and at pH = 3.1
there are twice as many H+ ions present that at pH = 3.4. The pH is measured
potentiometrically – i.e. by currentless potential measurements. Apart from the
measuring instrument (pH meter or titrator), a pH glass electrode and a refer-
ence electrode are required. For practical reasons these two electrodes are
usually contained in a single combined electrode.
According to Nernst (we will not go into any details here) the theoretical slope
of such electrodes is 59.2 mV / pH at 25 °C or 58.2 mV / pH at 20 °C. The elec-
trode zero point (0 mV) normally lies at pH = 7.0, but can vary within certain
limits without the measuring accuracy being affected. This variation called pHas
(asymmetry) should not exceed ±0.25 pH units. As a result of aging processes
the electrode slope diminishes with time. If it becomes lower than 92% of the
theoretical slope, i.e. 54.5 mV / pH at 25 °C or 53.5 mV / pH at 20 °C then the
electrode must be regenerated (send it to your local Metrohm agency).
1
Method 1 –
In order to check the condition of the electrode and to set the electrode data on
the measuring instrument, the electrode is calibrated with pH buffer solutions.
Buffer solutions are standards that have a defined pH value. This pH value is
also temperature-dependent and this temperature dependency is given on the
label of commercial buffer solutions. The relationship can be seen in the plot of
«mV against pH»:
--- Theoretical values
0 mV at pH = 7.00 and T = 25 °C
Slope = 59.2 mV / pH (100%)
+177.6 mV at pH = 4.00 and
+414.4 mV at pH = 0.00
–177.6 mV at pH = 10.00 and
–414.4 mV at pH = 14.00
--- Example with practical values

0 mV at pH = 6.85 and T = 25 °C
(–8.9 mV at pH = 7.00)
Slope = 56.3 mV / pH (95.1%)
+160.0 mV at pH = 4.00 and
+385.2 mV at pH = 0.00
–177.8 mV at pH = 10.00 and
–403.0 mV at pH = 14.00
A pH value
The asymmetry potential

is determined by using
the buffer solution pH = 7.00; a second buffer solution is used to determine the
slope of the pH electrode. It is important that at least one buffer value is located
close to that expected for the sample. From the asymmetry potential and slope
the pH meter determines the calibration line for the pH electrode and uses it to
convert the measured mV values into pH values.
2
Method 1 –
Practical work Always use fresh buffer solutions – after use these should be discarded and not
returned to the bottle!
We recommend the use of a pH electrode with built-in temperature sensor
– 6.0258.000 Unitrode.
A) According to Au/CH/
RSA/SA (two-point cali- tCR
'0$4ITRINO
bration) DATE TIME
Connect the electrode to MEASINPUT#!,-
CALDATE
the Titrino, rinse it with P(5M6
dist. H2O and dab it dry BUFFER
with a soft paper tissue. BUFFER
CAL4EMP#
Immerse the electrode SLOPEREL P(AS
in the first Metrohm
buffer solution, switch tPA
on the stirrer, select '0$4ITRINO
<CAL> mode and press DATE TIME
CALP(-
<START>. Enter the set PARAMETERS
A pH value
value of the first buffer CALIBRATIONPARAMETERS
solution, e.g. 7.00 at 25 MEASINPUT
CALTEMP#
°C (7.02 at 20 °C) and BUFFERP(
accept the value with BUFFERP(
<ENTER>. The buffer BUFFERP(/&&
is measured. Rinse the SIGNALDRIFTM6MIN
EQUILIBRTIMES
electrode with dist. H2O, ELECTRID
dab it dry, immerse it in SAMPLECHANGERCAL/&&
the second buffer solu- ACTIVATEPULSE/&&
LIMITSMPLSIZE/&&
tion, stir, enter the set STATISTICS
value for the second buf- STATUS/&&
fer solution, e.g. 4.00 at
25 °C (3.99 at 20 °C) and
accept the value with
<ENTER>. The second
buffer solution is mea-
sured. Exit the calibration
mode with <STOP>.
The calibration data can
be viewed with <CAL:
DATA>. The key se-
quence <PRINT><CAL:
DATA><ENTER> is
used to print out the cali-
bration report.
3
Method 1 –
B) According to the EU
tCR (two-point calibration)
'0$4ITRINO
DATE TIME Same procedure as for
MEASINPUT#!,- A). However, the DIN
CALDATE
P(5M6 buffer pH = 6.865 at 25
BUFFER °C (6.881 at 20 °C) and
BUFFER the buffer solution pH =
CALTEMP#
SLOPEREL P(AS 3.557 at 25 °C (3.57 at 20
°C) are used.
tPA
'0$4ITRINO
DATE TIME
#!,P(-
PARAMETERS
CALIBRATIONPARAMETERS
MEASINPUT
CALTEMP#
BUFFERP(
BUFFERP(
BUFFERP(/&&
SIGNALDRIFTM6MIN
A pH value
EQUILIBRTIMES
ELECTRID
SAMPLECHANGERCAL/&&
ACTIVATEPULSE/&&
LIMITSMPLSIZE/&&
STATISTICS
STATUS/&&

C) According to the USA

tCR (one-point calibration)
'0$4ITRINO
DATE TIME In this case only the buf-
MEASINPUT#!,- fer solution pH = 3.557
CALDATE
P(5M6 at 25 °C (3.57 at 20 °C)
BUFFER is used; after this buffer
BALTEMP# has been measured the
SLOPEREL P(AS
calibration mode is ex-
ited with <STOP>. The
tPA instrument then sets pH
'0$4ITRINO
DATE TIME
= 7.00 to 0 mV automati-
#!,P(- cally.
PARAMETERS
CALIBRATIONPARAMETERS
MEASINPUT
CALTEMP#
BUFFERP(
BUFFERP(/&&
BUFFERP(/&&
SIGNALDRIFTM6MIN
EQUILIBRTIMES
ELECTRID
SAMPLECHANGERCAL/&&
ACTIVATEPULSE/&&
LIMITSMPLSIZE/&&
STATISTICS
STATUS/&&

4
Method 2 –
A 2 Measuring the pH value
Rinse the electrode with dist. H2O and dab it dry with a soft paper tissue. Im-
merse the electrode in the undiluted wine sample and measure the pH under
stirring. When the drift criterion has been achieved, the pH value will be shown
on the instrument or printed out. The measured pH is stored in the Titrino as the
constant C40.
Presentation of the Au/RSA/USA to ±0.03 pH

results EU to ±0.02 pH
CH to ±0.05 pH
SA no information
Rinse the electrode with dist. H2O and dab it dry. If it is not to be used again the
electrode is stored in the electrolyte solution c(KCl) = 3 mol/L.
Remarks The pH value is of great importance for biological systems. In wines it plays
a larger role than the titratable total acidity. The pH influences the growth of
microorganisms, the color and shade, taste, redox potential, the ratio of free to
A pH value
bound SO2, the stability, the possibility of forming or preventing iron phosphate
turbidity, etc. There is no direct relationship between the pH value and the
content of titratable total acidity; in contrast, there is an (empirical) relationship
between the pH value and the potassium hydrogen tartrate / tartaric acid ratio.
The pH of a solution (wine) is also temperature-dependent. This temperature
dependency cannot be compensated by the instrument, which only adjusts the
electrode slope! This means that, when giving the pH value, it is essential that
the temperature at which the pH was measured is also mentioned. Example:
pH = 3.52 at 18.2 °C.
The pH value of wines is normally in the range 3.3 to 3.8:
Table wines 3.1...3.6; sparkling wines 3.0...3.6; dessert wines and late-vintage
wines 3.4...3.8.
tFR tFR tFR

'0$4ITRINO '0$4ITRINO '0$4ITRINO

USER USER USER
DATE TIME DATE TIME DATE TIME

-%!3 -%!3 -%!3
P(- P(- P(-
# # #

red wine white wine sparkling wine
1
Method 3 –
B 1 Preparation and titer determination of the
titrant
Recommended acces- • 6.3014.223 or 6.3026.220 Exchange Unit (possibly with 6.1608.040 PE bot-
sories tle)
• 6.0258.000 Unitrode (comb. pH glass electrode with built-in Pt 1000 tem-
perature sensor)
• Alternatively: 6.0259.100 Unitrode (comb. pH glass electrode) with 6.2104.020
Reagents • Titrant: c(NaOH) = 0.1 mol/L, e.g. Merck no. 109141, or dissolve 4.0 g NaOH
in CO2-free dist. H2O, make up to 1000 mL and mix.
• Standard substance: potassium hydrogen phthalate, e.g. Merck no. 102400

General The titrant c(NaOH) = 0.1 mol/L is available commercially as a ready-to-use
solution, its titer has been adjusted by the manufacturer to 1.000 at 20 °C. We
recommend the use of such a titrant. The titer of NaOH solutions is not stable
(CO2 absorption from the air). To prevent this absorption as far as possible,
soda lime (e.g. Merck no. 106839) should be filled into the drying/absorber tube
of the Exchange Unit.
The titer is determined by comparison with so-called standard substances.
These hardly change their content at all, are available with a defined degree
of purity, can be dried and are directly traceable to standard reference materi-
als (e.g. National Institute of Standards and Technology – NIST, USA). Such a
standard substance (secondary standard) is potassium hydrogen phthalate,
M = 204.23 g/mol.
Titer determination Potassium hydrogen phthalate is dried overnight in a drying oven at 105 °C and
allowed to cool down in a desiccator for at least 1 h. Care should be taken that
the titrations are carried out at a constant temperature.
The titer determination is normally carried out three times and the mean value is
used. The mean value of the titer is stored in the Titrino, e.g. as Common Vari-
able C30.
Approx. 200 mg KH phthalate is weighed out into the titration beaker with an
accuracy of 0.1 mg and dissolved in approx. 50 mL dist. H2O. The solution is im-
mediately titrated against c(NaOH) = 0.1 mol/L until after the first endpoint.
1 mL c(NaOH) = 0.1 mol/L corresponds to 20.423 mg KH phthalate
Calculation of the Titer = C00 / C01 / EP1

titer EP1 = mL NaOH consumed to reach the endpoint
C00 = weight of KH phthalate in mg
C01 = 20.423
1
Method 3 –
titrant
Method parameters and calculation Titration curve
tPA
'0$4ITRINO
DATE TIME
$%45-
PARAMETERS
TITRATIONPARAMETERS
MEASPTDENSITY
MININCR±L
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/.
MEANN
RESTABORIGINAL
EVALUATION
%0#
%0RECOGNITIONALL
lX%0AT5/&&M6
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZEVALUE
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
$%45-
DEF
FORMULA
4ITER##%0
23TEXT4ITER
23DECIMALPLACES
23UNIT
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
REPORT#/-FULLCURVEPARAM
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
$%45-
# FMLA
#

2
Method 3 –
titrant
tPA
'0$4ITRINO
DATE TIME
$%45-
PARAMETERS
TITRATIONPARAMETERS
MEASPTDENSITY
MININCR±L
DOSRATEMAXMLMIN

SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/.
MEANN
RESTABORIGINAL
EVALUATION
%0#
%0RECOGNITIONALL
lX%0AT5/&&M6
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZEVALUE
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
$%45-
DEF
FORMULA
4ITER##%0
23TEXT4ITER
23DECIMALPLACES
23UNIT
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
$%45-
# FMLA
#

3
Method 3 –
titrant
tPA
'0$4ITRINO
DATE TIME
$%45-
PARAMETERS
TITRATIONPARAMETERS
MEASPTDENSITY
MININCR±L
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/.
MEANN
RESTABORIGINAL
EVALUATION
%0#
%0RECOGNITIONALL
lX%0AT5/&&M6
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZEVALUE
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
$%45-
DEF
FORMULA
4ITER##%0
23TEXT4ITER
23DECIMALPLACES
23UNIT
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
$%45-
# FMLA
#

4
Method 4 –
B 2 Titration procedures for the determination
of the total titratable acidity
Recommended • 6.3014.223 or 6.3026.220 Exchange Unit (possibly with 6.1608.040 PE bot-

accessories tle)
• 6.0258.000 Unitrode (comb. pH glass electrode with built-in Pt 1000 tem-
perature sensor)
Alternatively: 6.0259.100 Unitrode (comb. pH glass electrode) with 6.2104.020
Reagents • Titrant: c(NaOH) = 0.1 mol/L (method 3)

• Possibly nitrogen from a pressure cylinder

The total titratable acidity is understood to be that fraction of acids contained in
the must and/or wine (with the exception of carbonic acid) that are determined
when the must is neutralized with NaOH to an agreed or predefined pH value.
These titratable acids are mainly weak acids (tartaric acid, malic acid, etc.).
Their neutral point is above pH = 7.0 (at approx. pH = 8.2). It is therefore obvi-
ous that lower values will be obtained by titrating to pH = 7.0 than when titrating
to pH = 8.2. To be able to compare the analytical values it is essential that the
titration is carried out to the agreed pH value. As this latter is defined differently,
it is best to record the whole titration curve and to allow the titrant consumption
up to the given pH value to be recalculated (by the titrator).
CH, EU, Israel and RSA Titration to pH = 7.0
Au and USA Titration to pH = 8.2 or to the point of inflection
General procedure The sample is degassed by passing nitrogen through it, by briefly boiling and
cooling it down rapidly or under vacuum (CO2 removal). The given sample vol-
ume is diluted with CO2-free dist. H2O and titrated immediately with c(NaOH) =
0.1 mol/L.
Detailed procedures A) CH, EU, Israel, RSA

Titrate 10 mL degassed sample plus 10 mL dist. H2O (CO2-free) with c(NaOH)
= 0.1 mol/L up to pH = 7.0.
B) Au
= 0.1 mol/L up to pH = 8.2 or, preferably, to the inflection point of the titration
curve.
C) USA
= 0.1 mol/L up to pH = 8.2 or, preferably, to the inflection point of the titration
curve.
D) SA
Titrate 20 mL degassed sample with c(NaOH) = 0.1 mol/L up to pH = 7.0. Re-
sult also given in g/L H2SO4.
1
Method 4 –
The total titratable acidity is usually given in g/L tartaric acid (exception USA; Calculation
g/100 mL) and/or in milliequivalents (meq.) per liter.
g/L tartaric acid = EPn x C30 x 7.5 / C00
g/L sulfuric acid = g/L tartaric acid x 0.653
g/100 mL tartaric acid = EPn x C30 x 0.75 / C00
meq./L = EPn x C30 x 0.1 x 1000 / C00

= EPn x C30 x 100 / C00
EPn = mL NaOH up to pH = 7.0 or pH = 8.2 or up to the inflection point of the curve
C00 = sample volume in mL

C30 = titer of the NaOH solution used (method 3)
7.5 = equivalent weight of tartaric acid
The determination of the total titratable acidity is important for:

Remarks
– musts, to be able to adjust the acidity and add the correct amount of SO2;
– wines, to be able to follow the change in pH and the tartaric acid concentra-
tion.
After acid degradation the values for the total titratable acidity normally lie be-
tween 4.0 and 6.5 g/L (red wines 4.0...5.5 g/L, «dry» wines 6.0...9.0 g/L).
2
Method 4 –
Method parameters and calculation method A – red wine
tPA tDE
'0$4ITRINO '0$4ITRINO
DATE TIME DATE TIME
$%4P(- $%45-
PARAMETERS DEF
TITRATIONPARAMETERS FORMULA
MEASPTDENSITY 7EINS%0
#
##
MININCR±L 23TEXT7EINS
DOSRATEMAXMLMIN 23DECIMALPLACES

SIGNALDRIFTM6MIN 23UNITGL
EQUILIBRTIMES 23LIMITCONTROL/&&
START6/&& (3/23
#
PAUSES 23TEXT(3/
DOSELEMENTINTERNAL$ 23DECIMALPLACES
MEASINPUT 23UNITGL
TEMPERATURE# 23LIMITCONTROL/&&
STOPCONDITIONS 7EINS%0
#
##
STOP6ABS 23TEXT7EINS
STOP6ML 23DECIMALPLACES
STOPP(/&& 23UNITGL
STOP%0 23LIMITCONTROL/&&
lLLINGRATEMAXMLMIN 'ESAMTS%0
#
#
##
STATISTICS 23TEXT'ESAMTS
STATUS/&& 23DECIMALPLACES
EVALUATION 23UNITMEQL
%0# 23LIMITCONTROL/&&
%0RECOGNITION/&& SILOCALCULATIONS
lX%0ATP( MATCHID/&&
lX%0ATP(/&& COMMONVARIABLES
P+(.0/&& REPORT
PRESELECTIONS REPORT#/-FULLCURVEPARAM
REQIDENT/&& MEAN
REQSMPLSIZE/&& -.23
LIMITSMPLSIZE/&& TEMPORARYVARIABLES
ACTIVATEPULSE/&&
tCF
'0$4ITRINO
DATE TIME
$%45-
C FMLA
#
#
#
#
Titration curve method A – red wine #

Result method A – red wine
tFR
'0$4ITRINO
USER
DATE TIME
P(CINIT $%4P(
lX%0ML
STOP6REACHED

3
Method 4 –
Method parameters and calculation method A – white wine
tPA tDE
DATE TIME DATE TIME
$%4P(
$%4P(-
PARAMETERS DEF
#
##
START6/&& (3/23
#
PAUSES 23TEXT(3/
MEASINPUT 23UNITGL
#
##
STOPP(/&& 23UNITGL
#
#
##
lX%0ATP( MATCHID/&&
P+(.0/&& REPORT
REQIDENT/&& MEAN
REQSMPLSIZE/&& -.23
ACTIVATEPULSE/&&
tCF
'0$4ITRINO
DATE TIME
$%4P(-
C FMLA
#
#
#
#
Titration curve method A – white wine #

Result method A – white wine
tFR
'0$4ITRINO
USER
DATE TIME
P(CINIT $%4P(
lX%0ML
STOP6REACHED

4
Method 4 –
Method parameters and calculation method B – red wine
tPA tDE
DATE TIME DATE TIME
$%4P(
$%4P(-
PARAMETERS DEF
#
##

START6/&& (3/23
#
PAUSES 23TEXT(3/
MEASINPUT 23UNITGL
#
##
STOPP(/&& 23UNITGL
#
#
##
lX%0ATP( MATCHID/&&
P+(.0/&& REPORT
REQIDENT/&& MEAN
REQSMPLSIZE/&& -.23
ACTIVATEPULSE/&&
tCF
'0$4ITRINO
DATE TIME
$%4P(-
C FMLA
#
#
#
#
Titration curve method B – red wine #

Result method B – red wine
tFR
'0$4ITRINO
USER
DATE TIME
P(CINIT $%4P(
lX%0ML
STOP6REACHED

5
Method 4 –
Method parameters and calculation method B – white wine
tPA tDE
DATE TIME DATE TIME
$%4P(
$%4P(-
PARAMETERS DEF
#
##
START6/&& (3/23
#
PAUSES 23TEXT(3/
MEASINPUT 23UNITGL
#
##
STOPP(/&& 23UNITGL
#
#
##
lX%0ATP( MATCHID/&&
P+(.0/&& REPORT
REQIDENT/&& MEAN
REQSMPLSIZE/&& -.23
ACTIVATEPULSE/&&
tCF
'0$4ITRINO
DATE TIME
$%4P(-
C FMLA
#
#
#
#
Titration curve method B – white wine #

Result method B – white wine
tFR
'0$4ITRINO
USER
DATE TIME
P(CINIT $%4P(
lX%0ML
STOP6REACHED

6
Method 4 –
Method parameters and calculation method C – red wine
tPA tDE
DATE TIME DATE TIME
$%4P(
$%4P(-
PARAMETERS DEF
#
##

START6/&& (3/23
#
PAUSES 23TEXT(3/
MEASINPUT 23UNITGL
#
##
STOPP(/&& 23UNITGL
#
#
##
lX%0ATP( MATCHID/&&
P+(.0/&& REPORT
REQIDENT/&& MEAN
REQSMPLSIZE/&& -.23
ACTIVATEPULSE/&&
tCF
'0$4ITRINO
DATE TIME
$%4P(-
C FMLA
#
#
#
#
Titration curve method C – red wine #

Result method C – red wine
tFR
'0$4ITRINO
USER
DATE TIME
P(CINIT $%4P(
lX%0ML
STOP6REACHED

7
Method 4 –
Method parameters and calculation method C – white wine
tPA tDE
DATE TIME DATE TIME
$%4P(
$%45-
PARAMETERS DEF
#
##
START6/&& (3/23
#
PAUSES 23TEXT(3/
MEASINPUT 23UNITGL
#
##
STOPP(/&& 23UNITGL
#
#
##
lX%0ATP( MATCHID/&&
P+(.0/&& REPORT
REQIDENT/&& MEAN
REQSMPLSIZE/&& -.23
ACTIVATEPULSE/&&
tCF
'0$4ITRINO
DATE TIME
$%45-
C FMLA
#
#
#
#
Titration curve method C – white wine #

Result method C – white wine
tFR
'0$4ITRINO
USER
DATE TIME
P(CINIT $%4P(
lX%0ML
STOP6REACHED

8
Method 4 –
Method parameters and calculation method D – red wine
tPA tDE
USER DATE TIME
DATE TIME $%4P(-
$%4P(- DEF
PARAMETERS FORMULA
TITRATIONPARAMETERS 7EINS%0
#
##
MEASPTDENSITY 23TEXT7EINS
MININCR±L 23DECIMALPLACES

DOSRATEMAXMLMIN 23UNITGL
SIGNALDRIFTM6MIN 23LIMITCONTROL/&&
EQUILIBRTIMES (3/23
#
START6/&& 23TEXT(3/
PAUSES 23DECIMALPLACES
DOSELEMENTINTERNAL$ 23UNITGL
MEASINPUT 23LIMITCONTROL/&&
TEMPERATURE# 7EINS%0
#
##
STOPCONDITIONS 23TEXT7EINS
STOP6ABS 23DECIMALPLACES
STOP6ML 23UNITGL
STOPP(/&& 23LIMITCONTROL/&&
STOP%0 'ESAMTS%0
#
#
##
lLLINGRATEMAXMLMIN 23TEXT'ESAMTS
STATISTICS 23DECIMALPLACES
STATUS/&& 23UNITMEQL
EVALUATION 23LIMITCONTROL/&&
%0# SILOCALCULATIONS
%0RECOGNITION/&& MATCHID/&&
lX%0ATP( COMMONVARIABLES
lX%0ATP(/&& REPORT
P+(.0/&& REPORT#/-FULLCURVEPARAM
PRESELECTIONS MEAN
REQIDENT/&& -.23
REQSMPLSIZE/&& TEMPORARYVARIABLES
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&& tCF
'0$4ITRINO
DATE TIME
$%4P(-
C FMLA
#
#
#
#
Titration curve method D – red wine #

Result method D – red wine
tFR
'0$4ITRINO
USER
DATE TIME
P(CINIT $%4P(
lX%0ML
STOP6REACHED

9
Method 4 –
Method parameters and calculation method D – white wine
tPA tDE
USER DATE TIME
DATE TIME $%45-
$%4P(- DEF
PARAMETERS FORMULA
TITRATIONPARAMETERS 7EINS%0
#
##
MEASPTDENSITY 23TEXT7EINS
MININCR±L 23DECIMALPLACES
DOSRATEMAXMLMIN 23UNITGL
SIGNALDRIFTM6MIN 23LIMITCONTROL/&&
EQUILIBRTIMES (3/23
#
START6/&& 23TEXT(3/
PAUSES 23DECIMALPLACES
DOSELEMENTINTERNAL$ 23UNITGL
MEASINPUT 23LIMITCONTROL/&&
TEMPERATURE# 7EINS%0
#
##
STOPCONDITIONS 23TEXT7EINS
STOP6ABS 23DECIMALPLACES
STOP6ML 23UNITGL
STOPP(/&& 23LIMITCONTROL/&&
STOP%0 'ESAMTS%0
#
#
##
lLLINGRATEMAXMLMIN 23TEXT'ESAMTS
STATISTICS 23DECIMALPLACES
STATUS/&& 23UNITMEQL
EVALUATION 23LIMITCONTROL/&&
%0# SILOCALCULATIONS
%0RECOGNITION/&& MATCHID/&&
lX%0ATP( COMMONVARIABLES
lX%0ATP(/&& REPORT
P+(.0/&& REPORT#/-FULLCURVEPARAM
PRESELECTIONS MEAN
REQIDENT/&& -.23
REQSMPLSIZE/&& TEMPORARYVARIABLES
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&& tCF
'0$4ITRINO
DATE TIME
$%45-
C FMLA
#
#
#
#
Titration curve method D – white wine #

Result method D – white wine
tFR
'0$4ITRINO
USER
DATE TIME
P(CINIT $%4P(
lX%0ML
STOP6REACHED

10
Method 5 –
C 1 Preparation and titer determination of the
titrant
Recommended • 6.3014.223 or 6.3026.220 Exchange Units

accessories • 6.0259.100 Unitrode
• 6.0309.100 double Pt-sheet electrode
• 6.2104.020 electrode cable
Reagents • Titrant I: c(NaOH) = 0.01 mol/L, e.g. Titrisol, Merck no. 109961, or dissolve
0.40 g NaOH in CO2-free dist. H2O, make up to 1000 mL and mix.
• Standard substance: potassium hydrogen phthalate, e.g. Merck no. 102400
C Free sulfurous acid (SO2)

• Titrant II: c(I2) = 0.01 mol/L (0.02 N). Make up 200 mL c(I2) = 0.05
mol/L, e.g. Merck no. 109099, to 1000 mL with dist. H2O and mix.
Alternatively: Dissolve 4...5 g potassium iodide, e.g. Merck no. 105043, in
approx. 10 mL dist. H2O in a 1000 mL round-bottomed flask and add 2.55 g
iodine, e.g. Merck no. 104761. The sealed flask is shaken, without the addi-
tion of any more water, until all the iodine has dissolved. The solution is then
made up to the mark with dist. H2O and mixed.
• Titrant III: Iodide-iodate solution, c(I 2 ) = 1/128 mol/L (N/64), e.g. Titrisol,
Merck no. 109099, or dissolve 0.5573 g potassium iodate (dried at max.
150 °C), e.g. Merck no. 105051, in approx. 700 mL dist. H2O. Add 3.5 g potas-
sium iodide, e.g. Merck no. 105043, and dissolve; make up to 1000 mL with
dist. H2O and mix.
• Sulfite standard: Weigh out 102.0 mg Na 2SO3 w = 98%, e.g. Merck no.
106657, into a 100 mL volumetric flask, dissolve in O2-free dist. H2O, then
make up to the mark and mix.
1 mL standard contains 1 mg Na 2SO3
As the solution is not stable, it must be prepared immediately before use.
• Sulfuric acid: w(H2SO4) = 25%, e.g. Merck no. 100716
• Sodium hydrogen carbonate: NaHCO3, e.g. Merck no. 106329
• Potassium iodide: KI, e.g. Merck no. 159226
General The titrants c(NaOH) = 0.01 mol/L and c(I2) = 1/128 mol/L are commercially
available as ready-to-use solutions; their titers have been adjusted by the manu-
facturer to 1.000 at 20 °C. We recommend the use of such titrants. In contrast,
you must prepare the titrant c(I2) = 0.01 mol/L yourself.
Many titrants are unstable, which means that the titer must be checked regu-
larly. This is done by comparison with so-called standard substances. These
hardly change their content at all, are available with a defined degree of purity,
can be dried and are directly traceable to standard reference materials (e.g.
National Institute of Standards and Technology – NIST, USA). Such a standard
substance (secondary standard) is potassium hydrogen phthalate, M = 204.23
g/mol. Unfortunately no such standard substance exists for the direct titer
determination of the iodine solutions. You must prepare the sulfite standard
solution yourself. This is done by using a substance whose minimum content is
guaranteed by the manufacturer. The small error of approx. 1% that could occur
can, in our opinion, be neglected.
1
Method 5 –
titrant
C 1.1 c(NaOH) = 0.01 mol/L

This titrant is unstable as it absorbs CO2 from the atmosphere. To prevent f this
absorption as far as possible, soda lime (e.g. Merck no. 106839) is filled into the
drying/absorber tube of the Exchange Unit.
Potassium hydrogen phthalate is dried overnight in a drying oven at 105 °C and Titer determination
allowed to cool down in a desiccator for at least 1 h. Care should be taken that
the titrations are carried out at a constant temperature.
able C31.
Approx. 20 mg KH phthalate is weighed out into the titration beaker with an
accuracy of 0.1 mg and dissolved in approx. 30 mL dist. H2O. The solution is
immediately titrated with c(NaOH) = 0.01 mol/L until after the first endpoint
(Unitrode).
1 mL c(NaOH) = 0.01 mol/L corresponds to 2.0423 mg KH phthalate
Titer = C00 / C01 / EP1 Calculation of titer

EP1 = mL NaOH consumed up to the endpoint
C00 = weight of KH phthalate in mg
C01 = 2.0432
2
Method 5 –
titrant
tPA
'0$4ITRINO
DATE TIME
$%45-
PARAMETERS
TITRATIONPARAMETERS
MEASPTDENSITY

MININCR±L
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/.
MEAN N
RESTABORIGINAL
EVALUATION
%0#
%0RECOGNITIONALL
lX%0AT5/&&M6
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZEVALUE
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
$%45-
DEF
FORMULA
4ITER##%0
23TEXT4ITER
23DECIMALPLACES
23UNIT
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
$%45-
# FMLA
#

3
Method 5 –
titrant
C 1.2 Orienting Ripper method c(I2) = 0.01 mol/L (0.02 N) Au, SA, USA
This titrant is unstable as iodine is volatile. We recommend that you determine
the titer of this titrant at least once per week. Care should be taken that the titra-
tions are carried out at a constant temperature.
able C32.
40 mL dist. H2O and 5.00 mL sulfite standard are placed in the titration bea-
ker. After the addition of 5 mL w(H2SO4) = 25% and approx. 1 g NaHCO3, the
solution is titrated with c(I2) = 0.01 mol/L up to the endpoint (double Pt-sheet
electrode).
1 mL c(I2) = 0.01 mol/L corresponds to 1.2604 mg Na2SO3
Titer = C00 / C01 / EP1 Calculation of titer

EP1 = mL iodine solution consumed up to the endpoint
C00 = 5 (weight of sulfite standard in mg)
C01 = 1.2604
4
Method 5 –
titrant
tPA
'0$4ITRINO
DATE TIME
$%4)POL-
PARAMETERS
TITRATIONPARAMETERS
MEASPTDENSITY

MININCR±L
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/&&
TEMPERATURE#
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/.
MEAN N
RESTABORIGINAL
EVALUATION
%0#
%0RECOGNITIONALL
lX%0AT5/&&M6
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
$%4)POL-
DEF
FORMULA
4ITER##%0
23TEXT4ITER
23DECIMALPLACES
23UNIT
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
$%4)POL-
# FMLA

5
Method 5 –
titrant
C 1.3 Orienting Ripper method c(I2) = 1/128 mol/L (N/64) CH, RSA
This titrant is relatively stable. Nevertheless, we recommend that you determine
the titer at least once per month. Care should be taken that the titrations are
carried out at a constant temperature.
able C32.
40 mL dist. H2O and 5.00 mL sulfite standard are placed in the titration beaker.
After the addition of approx. 1 g KI and 5 mL w(H2SO4) = 25% the solution is
titrated with c(I2) = 1/128 mol/L up to the endpoint (double Pt-sheet electrode).
1 mL c(I2) = 1/128 mol/L corresponds to 0.985 mg Na 2SO3
Calculation of titer
Titer = C00 / C01 / EP1
EP1 = mL iodide-iodate solution consumed up to the endpoint
C00 = 5 (weight of sufite standard in mg)
C01 = 0.985
6
Method 5 –
titrant
tPA
'0$4ITRINO
DATE TIME
-%4)POL-
PARAMETERS
TITRATIONPARAMETERS
6STEPML

DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/&&
TEMPERATURE#
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/.
MEAN N
RESTABORIGINAL
EVALUATION
%0#M6
%0RECOGNITIONALL
lX%0AT5/&&M6
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
-%4)POL-
DEF
FORMULA
4ITER##%0
23TEXT4ITER
23DECIMALPLACES
23UNIT
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tFM
'0$4ITRINO
DATE TIME
-%4)POL-
# FMLA
#

7
Method 6 –
C 2 Free sulfurous acid (SO2), orienting Ripper
method
Recommended • 6.3014.223 or 6.3026.220 Exchange Unit(s)

accessories • 6.0309.100 double Pt-sheet electrode
Reagents • Titrant II: c(I2) = 0.01 mol/L (0.02 N), method 5, Au, SA, USA
• Titrant III: iodide-iodate solution, c(I2) = 1/128 mol/L (N/64), method 5, CH,
RSA
• Sulfuric acid: w(H2SO4) = 25%

• Sodium hydrogen carbonate: NaHCO3
• Potassium iodide: KI
General Sulfite or sulfurous acid (SO2) is present in wines and musts in free and bound
form. Bound SO2 represents the main fraction of the total SO2. Sulfite is oxidized
to sulfate (sulfuric acid) by iodine.
A double Pt-sheet electrode that is polarized by applying a current (e.g. 1 μA) is
used for determining the endpoint. This is known as bivoltammetry (two elec-
trodes polarized by applying a current, the voltage is measured). As long as
an SO2 excess is present, the resulting voltage remains relatively high and ap-
proximately constant (about 300 mV). As soon as iodine is present in excess the
electrodes become depolarized and the voltage drops toward 0 mV (L-shaped
titration curve).
SO2 + H2O = H2SO3 (sulfurous acid)
H2SO3 + I2 + H2O = H2SO4 (sulfuric acid) + 2 HI
Regenerating the As a result of the oxidation of the platinum surfaces (new electrodes or elec-
trodes that have not been used for a long time) the electrode response be-
double Pt-sheet comes poorer. Either no voltage differences at all or only small ones are ob-
electrode tained. Mechanical cleaning has no effect. The electrode must be regenerated
electrochemically:
This is done by connecting the two platinum sheets to the minus pole of a DC
source (e.g. 4.5 V battery). A further platinum electrode or an iron nail (do not
use copper) is attached to the plus pole and both are immersed in a solution
of dilute sulfuric acid, to which a little sulfite can also be added. Electrolysis is
carried out under stirring for 3 min – gas bubbles should form on the electrode
surfaces. The electrodes are removed (still under current) and rinsed with dist.
H2O. This regeneration method is also described on the leaflet accompanying
the electrode.
General procedure Pipet the prescribed amount of sample into a beaker, add sulfuric acid and pos-
sibly NaHCO3 and KI and titrate with iodine solution up to the endpoint.
Detailed procedures A) Au, USA

Pipet 50 mL sample into a beaker, add 5 mL w(H2SO4) = 25% and approx. 1 g
NaHCO3 and titrate with c(I2) = 0.01 mol/L up to the endpoint.
B) SA
Pipet 10 mL sample and approx. 20 mL dist. H2O into a beaker, add 1 mL
w(H2SO4) = 25% and approx. 0.2 g NaHCO3 and titrate with c(I2) = 0.01 mol/L
up to the endpoint.
1
Method 6 –
method
C) CH, RSA
Pipet 50 mL sample into a beaker, add approx. 1 g KI and 5 mL w(H2SO4) = 25%
and titrate with c(I2) = 1/128 mol/L up to the endpoint.
The free sulfurous acid is given in mg SO2 per liter sample. Calculations
1 mL c(I2) = 0.01 mol/L corresponds to 0.641 mg SO2
1 mL c(I2) = 1/128 mol/L corresponds to 0.500 mg SO2
mg/L SO2 = EP1 x C01 x C32 x 1000 / C00
EP1 = mL titrant up to the endpoint

C00 = sample size in mL (50 or 10)
C01 = equivalent weight of SO2 (0.641 or 0.5)
C32 = titer of titrant (method 5)
• For sulfurization of the mash and the must, SO2 is added from a gas cylinder Remarks
or, less frequently, a potassium disulfite (K 2S2O5) solution is added. «Sulfu-
rous acid» is one of the most important must treatment agents. It is used
primarily for:
– Inhibiting or killing unwanted microorganisms
Acetic and lactic acid bacteria generally react more sensitively to the addi-
tion of SO2 than yeasts. The addition of 100 mg/L SO2 to the must delays
fermentation for only 1...2 days, but has the disadvantage that a large part
of the SO2 is bound to acetaldehyde by the yeasts, which means that the
total sulfurous acid balance is increased to an unacceptable level. As a
result only 40...50 mg/L SO2 are usually added.
– Inhibiting the oxidation enzymes (polyphenoloxidases)
These enzymes favor the formation of brown-colored entities by oxidation
of the natural colorants and tannins. In red wines this color loss could not
be remedied. Tyrosinase is deactivated to 90% by the addition of 40 mg/L
SO2 and to 100% by 80 mg/L SO2. The laccase (formed in rotten grapes
by the fungus Botrytis cinerea) is hardly deactivated by the addition of SO2
(brief heating to 70 °C).
• This method also determines ascorbic acid (vitamin C). This latter must be
determined separately and the result corrected accordingly.
• The maximum permissible amounts of free SO2 differ greatly according to the
local regulations and are in the range 5...70 mg/L SO2 (Greek white wine up
to 100 mg/L SO2). White wines normally have a higher SO2 content than red
wines.
2
Method 6 –
method
Method parameters for SET titration and calculation – Method A – red wine
tPA tFR
DATE TIME USER
3%4)POL- DATE TIME
PARAMETERS 5INIT M63%4)POL
3%4 SMPLSIZEML
%0AT5M6 %0MLM6

DYNAMICSM6 3/MGL
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

3
Method 6 –
method
Method parameters for SET titration and calculation – Method A – white wine
tPA tFR
DATE TIME USER
3%4)POL- DATE TIME
3%4 SMPLSIZEML
%0AT5M6 %0MLM6
DYNAMICSM6 3/MGL
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

4
Method 6 –
method
Method parameters for SET titration and calculation – Method A – sparkling wine
tPA tFR
DATE TIME USER
3%4)POL- DATE TIME
3%4 SMPLSIZEML
%0AT5M6 %0MLM6

DYNAMICSM6 3/MGL
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

5
Method 6 –
method
Method parameters for SET titration and calculation – Method B – red wine
tPA tFR
DATE TIME USER
3%4)POL- DATE TIME
3%4 SMPLSIZEML
%0AT5M6 %0MLM6
DYNAMICSM6 3/MGL
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

6
Method 6 –
method
Method parameters for SET titration and calculation – Method B – white wine
tPA tFR
DATE TIME USER
3%4)POL- DATE TIME
3%4 SMPLSIZEML
%0AT5M6 %0MLM6

DYNAMICSM6 3/MGL
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

7
Method 6 –
method
Method parameters for SET titration and calculation – Method B – sparkling wine
tPA tFR
DATE TIME USER
3%4)POL- DATE TIME
3%4 SMPLSIZEML
%0AT5M6 %0MLM6
DYNAMICSM6 3/MGL
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

8
Method 6 –
method
Method parameters for SET titration and calculation – Method C – red wine
tPA
'0$4ITRINO tFR
DATE TIME '044ITRINO
3%4)POL- DATE TIME
PARAMETERS 5INIT M63%4)POL-
3%4 SMPLSIZEML
%0AT5M6 %0MLM6

DYNAMICSM6 3/MG,
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

9
Method 6 –
method
Method parameters for SET titration and calculation – Method C – white wine
tPA tFR
DATE TIME USER
3%4)POL- DATE TIME
3%4 SMPLSIZEML
%0AT5M6 %0MLM6
DYNAMICSM6 3/MGL
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

10
Method 6 –
method
Method parameters for SET titration and calculation – Method C – sparkling wine
tPA
'0$4ITRINO tFR
DATE TIME '0$4ITRINO
3%4)POL- USER
PARAMETERS DATE TIME
3%4 5INIT M63%4)POL
%0AT5M6 SMPLSIZEML

DYNAMICSM6 %0MLM6
MAXRATEMLMIN 3/MG,
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
#-.
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

11
Method 7 –
C 3 Official reference method/distillation
method (Au, EU, Israel, RSA)
Recommended • 6.3014.223 or 6.3026.220 Exchange Unit

• Special setup, see figure «SO2» in the appendix
• Nitrogen from the pressure cylinder
Reagents • Titrant I: c(NaOH) = 0.01 mol/L (method 5)

• Absorption solution: w(H2O2) = 0.3%, preneutralized to pH = 8.1. 1.0 mL
w(H2O2) = 30% (e.g. Merck no. 107209) is filled up to 100 mL with dist. H2O
and adjusted to pH = 8.1 with c(NaOH) = 0.01 mol/L.
• Phosphoric acid: w(H3PO4) = 85% (e.g. Merck no. 100563)
General The sample is treated with H3PO4 in the special setup, a stream of nitrogen is
led through the solution at room temperature and transports the free SO2 into an
absorption solution (H2O2). The absorption solution oxidizes the SO2 to sulfuric
acid, which is then titrated with NaOH solution.
SO2 + H2O2 = H2SO4
Detailed regulations A) Au
Place 10 mL absorption solution into the absorption vessel and dilute with
10 mL dist. H2O. Add 10 mL H3PO4 and 20 mL sample to the round-bottomed
flask. Sparge nitrogen (1 L/min) through the solution for 15 min at room tem-
perature. The absorption solution is titrated with c(NaOH) = 0.01 mol/L to pH
= 8.1.
B) EU, Israel, RSA
Place 10 mL absorption solution into the absorption vessel and dilute with
10 mL dist. H2O. To the round-bottomed flask add 15 mL H3PO4 and 50 mL
sample for wines with an expected SO2 content <50 mg/L and 20 mL sample
for wines with an SO2 content >50 mg/L. Sparge nitrogen (1 L/min) through the
solution for 15 min at room temperature. The absorption solution is titrated with
c(NaOH) = 0.01 mol/L to pH = 8.1.
Calculations The free sulfurous acid is given in mg SO2 per liter sample.
1 mL c(NaOH) = 0.01 mol/L corresponds to 0.3203 mg SO2
mg/L SO2 = EP1 x C01 x C31 x 1000 / C00
EP1 = mL c(NaOH) = 0.01 mol/L up to the endpoint (pH = 8.1)
C01 = equivalent weight of SO2 (0.3203)
C31 = titer of NaOH (method 5)
1
Method 7 –
• For general remarks please refer to method 6. Remarks

• This method only determines SO2 and no other reductones (e.g. vitamin C).
The method is specific and suitable for determining the true SO 2 content.
• The NaOH used must be carbonate-free, as otherwise incorrect results will
be obtained (see under method 5).
• If the determination of the total sulfurous acid is to be carried out after this
method then the result should be stored in the Titrino, e.g. as Common Vari-
able C35.
2
Method 7 –
Method parameters of SET titration and calculation – Method A red wine
tPA tFR
USER USER
DATE TIME DATE TIME
3%4P(
P(CINIT 3%4P(
PARAMETERS SMPLSIZEML
3%4 %0ML

%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##
23TEXT3/
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
REPORT#/-FULLPARAMMPLISTCALC
MEAN
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

3
Method 7 –
Method parameters of SET titration and calculation – Method A white wine
tPA tFR
DATE TIME USER
3%4P(- DATE TIME
PARAMETERS P(CINIT 3%4P(
3%4 SMPLSIZEML
%0ATP( %0ML
DYNAMICS/&& 3/MG,
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##
23TEXT3/
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

4
Method 7 –
Method parameters of SET titration and calculation – Method A sparkling wine
tPA tFR
DATE TIME USER
3%4P(- DATE TIME
3%4 SMPLSIZEML
%0ATP( %0ML

DYNAMICS/&& 3/MG,
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##
23TEXT3/
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

5
Method 7 –
Method parameters of SET titration and calculation – Method B red wine
tPA tFR
USER USER
DATE TIME DATE TIME
3%4P(
P(CINIT 3%4P(-
3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##
23TEXT3/
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

6
Method 7 –
Method parameters of SET titration and calculation – Method B white wine
tPA tFR
DATE TIME USER
3%4P(- DATE TIME
3%4 SMPLSIZEML
%0ATP( %0ML

DYNAMICS/&& 3/MG,
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##
23TEXT3/
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

7
Method 7 –
Method parameters of SET titration and calculation – Method B sparkling wine
tPA tFR
DATE TIME USER
3%4P(- DATE TIME

3%4 SMPLSIZEML
%0ATP( %0ML
DYNAMICS/&& 3/MG,
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##
23TEXT3/
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

8
Method 8 –
D 1 Total sulfurous acid (SO2), orienting Ripper
method

Reagents • Titrant II: c(I2) = 0.01 mol/L (0.02 N), method 5, Au, SA, USA
• Titrant III: iodide-iodate solution, c(I2) = 1/128 mol/L (N/64), method 5, CH,
D Total sulfuric acid (total SO2)

RSA
• Sodium hydroxide: c(NaOH) = 1 mol/L
• Sulfuric acid: w(H2SO4) = 25%
• Sodium hydrogen carbonate: NaHCO3
• Potassium iodide: KI
General After alkaline hydrolysis, which releases the bound SO2, the total sulfurous acid
(free and bound SO2) is determined in the same way as the free sulfurous acid.
See also method 6.
General procedure Pipet the prescribed amount of sample into a beaker, add NaOH and allow to
react (hydrolyze) for 10 min. Add sulfuric acid and possibly NaHCO3 and KI and
titrate with iodine solution up to the endpoint.
Detailed procedures A) Au, USA

Pipet 20 mL sample into a beaker and add 25 mL c(NaOH) = 1 mol/L. Stir the
solution briefly and allow to react for 10 min. Add 10 mL w(H2SO4) = 25% and
approx. 1 g NaHCO3 and titrate with c(I2) = 0.01 mol/L up to the endpoint.
B) SA
Pipet 25 mL white wine or 10 mL red wine into a beaker and add 25 mL (10 mL)
c(NaOH) = 1 mol/L. Stir the solution briefly and allow to react for 10 min. Add
10 mL (4 mL) w(H2SO4) = 25% and approx. 0.2 g NaHCO3 and titrate with c(I2)
= 0.01 mol/L up to the endpoint.
C) CH, RSA
Pipet 50 mL sample into a beaker and add 25 mL c(NaOH) = 1 mol/L. Stir the
solution briefly and allow to react for 10 min. Add 10 mL w(H2SO4) = 25% and
approx. 1 g KI and titrate with c(I2) = 1/128 mol/L up to the endpoint.
Calculations The total free sulfurous acid is given in mg SO2 per liter sample.
1 mL c(I2) = 1/128 mol/L corresponds to 0.500 mg SO2
mg/L total SO2 = EP1 x C01 x C32 x 1000 / C00
EP1 = mL titrant up to the endpoint
C00 = sample size in mL (10…50)
C01 = equivalent weight of SO2 (0.641 or 0.5)
C32 = titer of titrant (method 5)
1
Method 8 –
method
• See also the remarks given for method 6 Remarks

• This method also determines ascorbic acid (vitamin C). This latter must be
determined separately and the result corrected accordingly.
• The maximum permissible amounts of total SO2 differ greatly according to
the local regulations and are in the range 40...300 mg/L SO2. White wines
normally have a higher SO2 content than red wines. With sweet wines, wine
made from selected grapes (Auslese) and late vintage wines (Spätlese) the
content can be up to 400 mg/L SO2 (up to 450 mg/L in Greece).
2
Method 8 –
method
Method parameters for SET titration and calculation – Method A red wine
tPA tFR
DATE TIME DATE TIME
3%4)POL- 5INIT M63%4)POL-

3%4 %0MLM6
%0AT5M6 3/MG,
DYNAMICSM6
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTION
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

3
Method 8 –
method
Method parameters for SET titration and calculation – Method A white wine
tPA tFR
DATE TIME DATE TIME
3%4 %0MLM6
%0AT5M6 3/MG,
DYNAMICSM6
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTION
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

4
Method 8 –
method
Method parameters for SET titration and calculation – Method B red wine
tPA tFR
DATE TIME DATE TIME

3%4 %0MLM6
%0AT5M6 3/MG,
DYNAMICSM6
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTION
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

5
Method 8 –
method
Method parameters for SET titration and calculation – Method B white wine
tPA tFR
DATE TIME DATE TIME
3%4 %0MLM6
%0AT5M6 3/MG,
DYNAMICSM6
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTION
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

6
Method 8 –
method
Method parameters for SET titration and calculation – Method C red wine
tPA tFR
DATE TIME DATE TIME

3%4 %0MLM6
%0AT5M6 3/MG,
DYNAMICSM6
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTION
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

7
Method 8 –
method
Method parameters for SET titration and calculation – Method C white wine
tPA tFR
DATE TIME DATE TIME
PARAMETERS %0MLM6
3%4 3/MG,
%0AT5M6
DYNAMICSM6
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS
TITRDIRECTION
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
)POL ±!
ELECTRODETEST/.
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4)POL-
# FMLA
#
#

8
Method 9 –
D 2 Official reference method / distillation
method (Au, CH, EU, Israel, RSA)

• Special setup, see figure «SO2» in the appendix
• Nitrogen from the pressure cylinder

• Absorption solution: w(H2O2) = 0.3%, preneutralized to pH = 8.1
(see method 7)
• Phosphoric acid: w(H3PO4) = 85%
• Methanol: CH3OH R (only CH)
General The determination of the total sulfurous acid is carried out after the determina-
tion of the free SO2. By sparging nitrogen through the boiling solution for 15 min,
the SO2 is driven out of the sample and transported to the absorption solution,
where the SO2 is oxidized to sulfuric acid by H2O2 and then titrated with NaOH.
Detailed procedure For sample weights and H3PO4 addition please see method 7.
A) Au
Place 10 mL absorption solution in the absorption vessel and dilute with 10 mL
dist. H2O. Sparge nitrogen (1 L/min) through the boiling solution for 15 min. The
absorption solution is titrated with c(NaOH) = 0.01 mol/L to pH = 8.1.
B) EU, Israel, RSA
dist. H2O. Sparge nitrogen (1 L/min) through the boiling solution for 15 min. The
absorption solution is titrated with c(NaOH) = 0.01 mol/L to pH = 8.1.
C) CH
dist. H2O. Transfer 50 mL each of H3PO4, methanol and sample into a round-
bottomed flask. Sparge nitrogen (1 L/min) through the solution, heat to boiling
and terminate this procedure after 15 min. The absorption solution is titrated
with c(NaOH) = 0.01 mol/L to pH = 8.1.
Calculations The total sulfurous acid is given in mg SO2 per liter sample.
1 mL c(NaOH) = 0.01 mol/L corresponds to 0.3203 mg SO2
Au, EU, Israel, RSA
mg/L total SO2 = C35 + (EP1 x C01 x C31 x 1000 / C00)
CH
mg/L total SO2 = EP1 x C01 x C31 x 1000 / C00
C31 = titer of NaOH (method 5)
C35 = Common Variable from method 7 (mg/L free SO2)
1
Method 9 –
See under methods 6 and 7. Remarks

2
Method 9 –
Method parameters and calculation – Method A red wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4P(-

3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

3
Method 9 –
Method parameters and calculation – Method A white wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4P(-
3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

4
Method 9 –
Method parameters and calculation – Method A sparkling wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4P(-

3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

5
Method 9 –
Method parameters and calculation – Method B red wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4P(-
3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

6
Method 9 –
Method parameters and calculation – Method B white wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4P(-

3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

7
Method 9 –
Method parameters and calculation – Method B sparkling wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4-
3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

8
Method 9 –
Method parameters and calculation – Method C red wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4P(-

3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

9
Method 9 –
Method parameters and calculation – Method C white wine
tPA tFR
DATE TIME $ATUM :EIT
3%4P(- P(INIT 3%4P(-
PARAMETERS %INMASSML
3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

10
Method 9 –
Method parameters and calculation – Method C sparkling wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4P(-

3%4 %0ML
%0ATP( 3/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
TIMEINTERVALS
STOPCONDITIONS
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
3/%0
#
#
##MGL
23TEXT3/
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

11
Method 10 –
Determination of volatile acidity

• 6.0309.100 double Pt-sheet electrode
• Steam distillation setup, see figure «Volatile acidity» in the appendix

• Titrant II: c(I2) = 0.01 mol/L (0.02 N) (method 5)
• Tartaric acid: C4H6O6, e.g. Merck no. 100802
• Sulfuric acid: w(H2SO4) = 25% (method 5)
• Hydrogen peroxide: w(H2O2) = 0.3% (preparation see method 7, the pH value
does not have to be adjusted). Normally only Au (Australia).
E Volatile acidity
General The determination of the volatile acidity is primarily concerned with determining the
lower fatty acids, which mainly consist of acetic acid, with only smaller amounts
of propionic, butyric and valeric acid being present. Under the sample treatment
conditions SO2 is also volatile and is determined separately after the NaOH titration
by iodometry; the value obtained is then subtracted from the apparent acetic acid
content. Sorbic acid – if present in the sample – is also determined and should be
taken into consideration when calculating the volatile acidity.
During normal fermentation only a small amount of acetic acid is produced
(0.1...0.9 g/L), with less in white wines than in red wines. An increased acetic
acid content gives the wine a «spoiled» taste (in which acetic acid ethyl ester
also participates). The increased content indicates that acetic acid formation
could start due to the presence of acetic acid bacteria. This is why it is important
to determine this parameter (volatile acidity).
General procedure Degas the wine sample to remove any CO2. Pipet the prescribed amount of
sample into the distillation flask, possibly add a small amount of tartaric acid
and/or H2O2 (H2O2 only Au) and subject the mixture to steam distillation until ap-
prox. 100 mL distillate has been collected. Titrate the distillate with NaOH to pH
= 8.2. Add sulfuric acid and titrate the SO2 in the distillate with iodine solution.
Detailed procedure CO2 removal

The sample is degassed by sparging nitrogen through it, by briefly boiling and
cooling it down rapidly or under vacuum (see also method 4).
A) CH, USA
Pipet 10 mL degassed sample into the round-bottomed flask. Connect the
steam generator and carry out steam distillation until there is approx. 100 mL
distillate in the receiver (lasts approx. 30 min). Titrate the distillate with c(NaOH)
= 0.1 mol/L to pH = 8.2. Add 5 mL w(H 2SO 4 ) = 25% and titrate with c(I 2 ) =
0.01 mol/L up to the endpoint (method 6).
B) EU
Pipet 20 mL degassed sample into the round-bottomed flask and add approx.
0.5 g tartaric acid. Connect the steam generator and carry out steam distillation
until there is approx. 100 mL distillate in the receiver. Titrate the distillate with
c(NaOH) = 0.1 mol/L to pH = 8.2. Add 5 mL w(H2SO4) = 25% and titrate with
c(I2) = 0.01 mol/L up to the endpoint (method 6).
1
Method 10 –
C) SA
Pipet 50 mL degassed sample into the round-bottomed flask and add approx.
0.5 g tartaric acid. Connect the steam generator and carry out steam distillation
until there is approx. 100 mL distillate in the receiver. Titrate the distillate with
c(NaOH) = 0.1 mol/L to pH = 8.2. Add 5 mL w(H2SO4) = 25% and titrate with
c(I2) = 0.01 mol/L up to the endpoint (method 6).
D) Au
Pipet 10 mL degassed sample and 0.5 mL H 2O 2 into the round-bottomed
flask. Connect the steam generator and carry out steam distillation until
there is approx. 100 mL distillate in the receiver. Titrate the distillate with
c(NaOH) = 0.1 mol/L to pH = 8.2 (in this method the SO2 is oxidized to sulfuric
acid by the addition H2O2 before the distillation and must not be determined).
The free acids are given as gram acetic acid per liter sample (USA: per 100 mL Calculations
E Volatile acidity
sample).
CH, EU, SA, USA
First calculate the SO2 content (mg/L) and store it in the Titrino, e.g. as «Com-
mon Variable» C36.
mg/L SO2 = EP1 x C01 x C32 / C00
EP1 = mL c(I2) = 0.01 mol/L up to the endpoint
C00 = sample size in mL (10, 20 or 50)
C32 = titer of iodine solution (method 5)
1 mg SO2 corresponds to a consumption of 0.3122 mL c(NaOH) = 0.1 mol/L or
1.875 mg acetic acid.
1 mL c(NaOH) = 0.1 mol/L corresponds to 6.005 mg acetic acid
g/L acetic acid = (EP1 x C01 x C30 */ C00) – (C36 x 1.875)
USA:
g/100 mL acetic acid = (EP1 x C01 x C30 x 0.1 / C00) – (C36 x 1.875)
C00 = sample size in mL (10, 20 or 50)
C01 = equivalent weight of acetic acid (6.005)
C30 = titer of NaOH solution (method 3)
C36 = mg/L SO2
Au
SO2 is oxidized to H2SO4 before the distillation by adding H2O2 and does not
have to be subtracted.
g/L acetic acid = EP1 x C01 x C30 / C00
• In the presence of sorbic acid a further correction must be made to the acetic Remarks
acid content (CH, USA). 1 g sorbic acid (C6H8O2) corresponds to 89.2 mL
c(NaOH) = 0.1 mol/L.
• If the SO2 is distilled over then the determination and calculation of the vola-
tile acids is complicated and time-consuming. This is why we recommend
the use of the Australian method (addition of H2O2 for oxidation of the SO2).
• The highest permissible amounts of volatile acids are in the range 0.11...0.12 g/L
acetic acid (for «heavy» red wines up to 0.8 g/L).
2
Method 10 –
Parameter report and calculations

Method 10.2 D
tPA Result of red wine

'044ITRINO
DATE TIME
3%4P(-ETH$
PARAMETERS
3%4 tFR
%0ATP( '044ITRINO
DYNAMICS/&& DATE TIME
MAXRATEMLMIN P(INIT 3%4P(-ETH$
MINRATE±LMIN SMPLSIZEML
STOPCRITDRIFT %0ML
STOPDRIFT±LMIN %SSIGSML
3%4
E Volatile acidity
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&& Result of white wine
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# tFR
TIMEINTERVALS '044ITRINO
STOPCONDITIONS DATE TIME
STOP6ABS P(INIT 3%4P(-ETH$
STOP6ML SMPLSIZEML
lLLINGRATEMAXMLMIN %0ML
STATISTICS %SSIGSML
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tCF
'044ITRINO
DATE TIME
3%4P(-ETH$
# FMLA
#

tDE
'044ITRINO
DATE TIME
3%4P(-ETH$
DEF
FORMULA
%SSIGS%0
#
##
23TEXT%SSIGS
23DECIMALPLACES
23UNITML
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
#
#23
REPORT
2EPORT#/-PARAMMP,ISTFULLCALC
MEAN
TEMPORARYVARIABLES

3
Method 10 –
Parameter report and calculations Parameter report and calculations

Method 10.1 Method 10.2
tPA tPA
'044ITRINO '044ITRINO
DATE TIME DATE TIME
3%4P(-ETH $%4)POL-ETH
PARAMETERS PARAMETERS
3%4 TITRATIONPARAMETERS
%0ATP( MEASPTDENSITY
DYNAMICS/&& MININCR±L
MAXRATEMLMIN DOSRATEMAXMLMIN
MINRATE±LMIN SIGNALDRIFTM6MIN
STOPCRITDRIFT EQUILIBRTIMES
STOPDRIFT±LMIN START6/&&
3%4 PAUSES
E Volatile acidity
%0ATP(/&& DOSELEMENTINTERNAL$
TITRATIONPARAMETERS )POL ±!
TITRDIRECTIONAUTO ELECTRODETEST/&&
PAUSES TEMPERATURE#
START6/&& STOPCONDITIONS
PAUSES STOP6ABS
EXTRTIMES STOP6ML
DOSELEMENTINTERNAL$ STOP5/&&M6
MEASINPUT STOP%0
TEMPERATURE# lLLINGRATEMAXMLMIN
TIMEINTERVALS STATISTICS
STOPCONDITIONS STATUS/&&
STOP6ABS EVALUATION
STOP6ML %0#
lLLINGRATEMAXMLMIN %0RECOGNITIONGREATEST
STATISTICS lX%0AT5/&&M6
STATUS/&& PRESELECTIONS
PRESELECTIONS REQIDENT/&&
CONDITIONING/&& REQSMPLSIZE/&&
REQIDENT/&& LIMITSMPLSIZE/&&
REQSMPLSIZE/&& ACTIVATEPULSE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&
tDE
'044ITRINO
tDE DATE TIME
'044ITRINO $%4)POL-ETH
DATE TIME DEF
3%4P(-ETH FORMULA
DEF 3/%0
#
##
FORMULA 23TEXT3/
.A/(%0 23DECIMALPLACES
23TEXT.A/( 23UNITMG,
23DECIMALPLACES 23LIMITCONTROL/&&
23UNITML %SSIGS#
#
## #
#
23LIMITCONTROL/&& 23TEXT%SSIGS
SILOCALCULATIONS 23DECIMALPLACES
MATCHID/&& 23UNITGL
COMMONVARIABLES 23LIMITCONTROL/&&
#23 SILOCALCULATIONS
REPORT MATCHID/&&
REPORT#/-PARAMMPLISTFULLCALC COMMONVARIABLES
MEAN #
TEMPORARYVARIABLES #
#23
REPORT
tCF REPORT#/-PARAMFULLMPLISTCALC
'044ITRINO MEAN
DATE TIME TEMPORARYVARIABLES
3%4P(-ETH
# FMLA

4
Method 10 –

Method 10.2
tCF
'044ITRINO
DATE TIME
$%4)POL-ETH
# FMLA
#
#
#

Result redwine – Method 10.2 A Result white wine – Method 10.2 A
E Volatile acidity
tFR tFR
DATE TIME DATE TIME
5INIT M6$%4)POL-ETH 5INIT M6$%4)POL-ETH
SMPLSIZEML SMPLSIZEML
%0MLM6 %0MLM6
3/MG, 3/MG,
%SSIGSGL %SSIGSGL
STOP6REACHED STOP6REACHED

Result red wine – Method 10.2 B Result white wine – Method 10.2 B
tFR tFR
DATE TIME DATE TIME
%0MLM6 %0MLM6
3/MG, 3/MG,
%SSIGSGL %SSIGSGL

Result red wine – Method 10.2 C Result white wine – Method 10.2 C
tFR tFR
DATE TIME DATE TIME
%0MLM6 %0MLM6
3/MG, 3/MG,
%SSIGSGL %SSIGSGL

5
Method 10 –

Method 10.2 D
tPA Result red wine

'044ITRINO
DATE TIME
3%4P(-ETH$
PARAMETERS
3%4 tFR
%0ATP( '044ITRINO
MAXRATEMLMIN P(INIT 3%4P(-ETH$
MINRATE±LMIN SMPLSIZEML
STOPCRITDRIFT %0ML
STOPDRIFT±LMIN %SSIGSML
3%4
E Volatile acidity
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTIONAUTO
PAUSES
START6/&& Result white wine
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# tFR
STOP6ABS P(INIT 3%4P(-ETH$
STOP6ML SMPLSIZEML
lLLINGRATEMAXMLMIN %0ML
STATISTICS %SSIGSML
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tCF
'044ITRINO
DATE TIME
3%4P(-ETH$
# FMLA
#

tDE
'044ITRINO
DATE TIME
3%4P(-ETH$
DEF
FORMULA
%SSIGS%0
#
##
23TEXT%SSIGS
23DECIMALPLACES
23UNITML
23LIMITCONTROL/&&
SILOCALCULATIONS
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COMMONVARIABLES
#
#23
REPORT
2EPORT#/-PARAMMP,ISTFULLCALC
MEAN
TEMPORARYVARIABLES

6
Method 11 –
Fixed acidity
The ﬁxed acidity is only determined in CH and the USA. It is obtained

by subtracting the volatile acidity (E, method 10) from the titratable total
acidity (B 2, method 4):
Fixed acidity = g/L B 2 – (1.25 x g/L E)
Examples: white and red wines according to method 10 (use the same
samples)
Red wine White wine
F Fixed acidity
tFR tFR
USER USER
DATE TIME DATE TIME
P(CINIT $%4P(- P(CINIT $%4P(-
SMPLSIZEG SMPLSIZEG
%0ML %0ML
%0ML %0ML
7EINSGL 7EINSGL
(3/GL (3/GL
7EINSGL 7EINSGL
'ESAMTSMEQL 'ESAMTSMEQL

tFR
'044ITRINO tFR
5INIT M6$%4)POL-ETH DATE TIME
SMPLSIZEML 5INIT M6$%4)POL-ETH
%0MLM6 SMPLSIZEML
3/MG, %0MLM6
%SSIGSGL 3/MG,
STOP6REACHED %SSIGSGL
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1
Method 12 –
Determination of ascorbic acid (vitamin C)

Reagents • Titrant II: c(I2) = 0.01 mol/L (0.02 N) (method 5)

• Glyoxal solution: w(glyoxal) = 40%. Transfer 200 mL glyoxal solution (40%,
e.g. Merck no. 820610) into a beaker and adjust the pH to 7.0 with c(NaOH)
= 1 mol/L. Store the solution in an amber bottle in a refrigerator.

• Sulfuric acid: w(H2SO4) = 25% (method 5)
General The ascorbic acid content of grapes and musts ranges from 5 to max. 150 mg/L.
This content is greatly reduced on fermentation. The ascorbic acid content of
wine is approx. 2 mg/L.
In some cases ascorbic acid is added because of its reductive properties.
However, this addition is limited to 150 mg/L! It is only carried out with reduc-
tive wines. 150 mg/L ascorbic acid can reduce the total SO2 content by max.
55 mg/L. No copper ions should be present in the wine as otherwise copper
turbidity will occur.
As the same titrant is used as for the SO2 determination (orienting Ripper meth-
od), the SO2 is also determined. This is the reason why glyoxal is added to the
sample to mask the SO2. (Note that the Ripper method, when used to determine
the SO2, also determines the ascorbic acid.)
Analysis 50 mL sample is measured into a beaker, treated with 2 mL glyoxal solution,

briefly stirred and allowed to stand for 5 min. After the addition of 5 mL w(H2SO4)
= 25% the solution is titrated with c(I2) = 0.01 mol/L up to the endpoint.
Calculations The ascorbic acid content is given in milligram per liter (USA: mg/100 mL).
1 mL c(I2) = 0.01 mol/L corresponds to 1.761 mg ascorbic acid (C6H8O6)
mg/L ascorbic acid = EP1 x C01 x C32 x 1000 / C00
mg/100 mL ascorbic acid = EP1 x C01 x C32 x 100 / C00
EP1 = mL iodine solution c(I2) = 0.01 mol/L up to the endpoint
C00 = sample size in mL (50)
C01 = equivalent weight of ascorbic acid (1.761)
C32 = titer of iodine solution (method 5)
Remarks • In some regulations dichlorophenol indophenol is proposed as the titrant.

This also determines SO2. In order to avoid a further (unstable) titrant we
titrate with the same iodine solution that is used for the determination of SO2.
This not only simplifies the titer determination, but also the calculation of the
SO2 content .
• The maximum permissible content of ascorbic acid is 150 mg/L in most
countries (CH up to 400 mg/L). The normal content is 1...10 mg/L.
1
Method 12 –
Parameter report and calculations for white wine without added ascorbic acid
tPA tCF
DATE TIME DATE TIME
3%4)POL- 3%4)POL-
PARAMETERS # FMLA
3%4 #
%0AT5M6 #
DYNAMICS/&&M6 #
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS Report
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES tFR
EXTRTIMES '0$4ITRINO
DOSELEMENTINTERNAL$ DATE TIME
)POL ±! 5INIT M63%4)POL-
ELECTRODETEST/&& SMPLSIZEML
TEMPERATURE# %0MLM6
TIMEINTERVALS !SCOBMG,
STOPCONDITIONS !SCORBMG
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
!SCORB%0
#
#
##MG,
23TEXT!SCORB
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
!SCORB%0
#
#
##MG
23TEXT!SCORB
23DECIMALPLACES
23UNIT MG
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

2
Method 12 –
Parameter report and calculations for white wine with added ascorbic acid (100 mg/L)
tPA tCF
DATE TIME DATE TIME
3%4)POL- 3%4)POL-
PARAMETERS # FMLA
3%4 #

%0AT5M6 #
DYNAMICS/&&M6 #
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITTIME
TDELAY S
3%4
%0AT5/&&M6
TITRATIONPARAMETERS Report
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES tFR
)POL ±! 5INIT M63%4)POL-
ELECTRODETEST/&& SMPLSIZEML
TEMPERATURE# %0MLM6
TIMEINTERVALS !SCORBMG,
STOPCONDITIONS !SCORBMG
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4)POL-
DEF
FORMULA
!SCORB%0
#
#
##MG,
23TEXT!SCORB
23DECIMALPLACES
23UNIT MGL
23LIMITCONTROL/&&
!SCORB%0
#
#
##MG
23TEXT!SCORB
23DECIMALPLACES
23UNIT MG
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

3
Method 13 –
H 1 Preparing the solutions and determination
of the calibration factor

accessories • 6.0431.100 Pt Titrode
• Possibly additional Dosimat, e.g. 2.776.0010
Reagents • Titrant: c(Na2S2O3) = 0.1 mol/L, e.g. Merck no. 109147 or alternatively: Weigh
out 24.818 g Na2S2O3 x 5 H2O (e.g. Merck no. 106516) into a 1000 mL volu-
metric flask and dissolve in approx. 500 mL dist. H2O. Add 25 mL c(NaOH) =
2 mol/L, make up to the mark with dist. H2O and mix.
• Sodium hydroxide solution: c(NaOH) = 2 mol/L. Weigh out 8 g NaOH (e.g.
Merck no. 106469) and dissolve in approx. 60 mL dist. H2O. After cooling
down make up to 100 mL with dist. H2O.
H Reducing sugars
• Sulfuric acid: w(H2SO4) = 16%. Under stirring carefully add 90 mL w(H2SO4)
= 98% (e.g. Merck no. 100713) to 800 mL dist. H2O. After cooling down make
up to 1000 mL.
• Potassium iodide solution: Weigh out 150 g KI (e.g. Merck no. 105040) into a
500 mL volumetric flask and dissolve in approx. 150 mL dist. H2O. Add 25 mL
c(NaOH) = 2 mol/L and make up to the mark with dist. H2O.
• Fehling’s solution 1: Weigh out 20.96 g CuSO4 x 5 H2O (e.g. Merck no.
102790) into a 500 mL volumetric flask and dissolve in approx. 250 mL dist.
H2O. Add 1 mL w(H2SO4) = 16%, make up to the mark with dist. H2O and
mix.
• Fehling’s solution 2: Weigh out 173 g potassium sodium tartrate tetrahydrate
(e.g. Merck no. 108087) into a beaker and dissolve in 200 mL dist. H2O.
Weigh out 40 g NaOH (e.g. Merck no. 106469) into a second beaker and dis-
solve in 200 mL dist. H2O. When the NaOH solution has cooled down, rinse
both solutions into a 500 mL volumetric flask with dist. H2O, make up to the
mark and mix.
• Glucose standards: Weigh out 1.0 g and 2.0 g glucose into two different 100
mL volumetric flasks, dissolve in dist. H2O, make up to the mark and mix. The
standards are not stable and should be prepared directly before use. They
correspond to 10 g/L and 20 g/L glucose, respectively.
General Reducing sugars contain either aldehyde, ketone or hemiacetal «end groups».
In must and wine the reducing sugars present are chiefly glucose and fructose.
During fermentation they are almost completely broken down by yeasts (in con-
trast, the pentoses, which are present in small amounts, are not fermented by
the yeasts). If fermentation is terminated prematurely then, of course, the reduc-
ing sugars content will be higher than in so-called «dry» wines.
In the analytical method described below an excess of Cu(II) ions is added to
the sample. Under heating these are reduced to Cu(I) ions by the reducing sug-
ars. The excess Cu(II) ions are treated with potassium iodide to form iodine and
further Cu(I) ions. The iodine produced is titrated with thiosulfate.
2 Cu2+ + 2 I – → 2 Cu+ + I2
I2 + 2 S2O32– → 2 I – + S4O62–
The oxidation of the sugars with Cu(II) – or the reduction of Cu(II) by the
sugars – takes place neither stoichiometrically nor linearly with time. This
is why a simple titer determination cannot be carried out, but rather a so-called
calibration factor must be determined by using glucose standards. Different
sample weights must be used to obtain meaningful values for wines with dif-
1
Method 13 –
ferent reducing sugar contents. This is done so that approximately the same
amount of reducing sugars is always present in the beaker under the same
conditions.
Reducing sugars are given as invert sugar. The conversion factor glucose/invert Determination of the
sugar is 1.8.
calibration factor
Blank value of the Cu solution
Pipet 2.0 mL dist. H2O, 10.00 mL Fehling’s solution 1 and 5 mL Fehling’s solu-
tion 2 into a beaker. Heat the mixture and boil it for exactly 30 s. Cool it down
immediately under running water. Add 10 mL each of potassium iodide solution,
w(H2SO4) = 16% and dist. H2O and titrate with c(Na2S2O3) = 0.1 mol/L until after
the first endpoint. The blank consumption is stored in the Titrino, e.g. as Com-
mon Variable C37.
H Reducing sugars
Glucose standard 10 g/L

Pipet 2.0 mL glucose standard 10 g/L into a beaker. Then proceed exactly as
described under «Blank value».
Glucose standard 20 g/L
Pipet 2.0 mL glucose standard 20 g/L into a beaker. Then proceed exactly as
described under «Blank value».
g/L reducing sugars = (C37 – EP1) x C02 Calculations

EP1 = mL thiosulfate solution consumed by the glucose standard
C02 = conversion factor glucose/invert sugar (1.8)
C37 = mL thiosulfate solution consumed in blank determination
Calibration factor
The calibration factor is calculated by dividing the given value for glucose (g/L)
by the found or calculated value for invert sugar (g/L). The mean value of the
two glucose standards is used a is stored in the Titrino, e.g. as Common Vari-
able C31.
Example:
Given: 10 g/L glucose 10 : 11.4 = 0.8772
Found: 11.4 g/L invert sugar
Given: 20 g/L glucose 20 : 21.8 = 0.9174
Found: 21.8 g/L invert sugar (0.8772 + 0.9174) : 2 =
0.8973 ±0.0201 = calibration factor
(C31)
• The boiling period of 30 s must be observed exactly as otherwise incorrect Remarks

results will be obtained. For the same reason, cooling down must occur im-
mediately after boiling.
• The method described above is an empirical method. It is never as accurate
as other titration methods. In the best case an error of approx. ±2.2% is to be
expected.
2
Method 13 –
Parameter report and Calculations

Method 13.1
tPA tCF
DATE TIME DATE TIME
$%45-ETH $%45-ETH
PARAMETERS # FMLA
TITRATIONPARAMETERS
MEASPTDENSITY
MININCR±L tDE
DOSRATEMAXMLMIN '044ITRINO
SIGNALDRIFTM6MIN DATE TIME
EQUILIBRTIMES $%45-ETH
START6/&& DEF
H Reducing sugars
PAUSES FORMULA
DOSELEMENTINTERNAL$ "LINDW%0
MEASINPUT 23TEXT"LINDW
TEMPERATURE# 23DECIMALPLACES
STOPCONDITIONS 23UNITM,
STOP6ABS 23LIMITCONTROL/&&
STOP6ML SILOCALCULATIONS
STOP5/&&M6 MATCHID/&&
STOP%0 COMMONVARIABLES
lLLINGRATEMAXMLMIN #23
STATISTICS REPORT
STATUS/&& REPORT#/-FULLMPLISTCALCPARAM
EVALUATION MEAN
%0# -.23
%0RECOGNITIONALL TEMPORARYVARIABLES
lX%0AT5/&&M6
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

3
Method 13 –
Parameter report and calculations Titration curve

Method 13.1 for glucose standard 20 g/L
tPA
'044ITRINO
DATE TIME
$%45-ETH
PARAMETERS
TITRATIONPARAMETERS
MEASPTDENSITY
MININCR±L
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
H Reducing sugars
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE#
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
EVALUATION
%0#
%0RECOGNITIONALL
lX%0AT5/&&M6
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tCF
'044ITRINO
DATE TIME
$%45-ETH
# FMLA
#

tDE
'044ITRINO
DATE >TIME
$%45-ETH
DEF
FORMULA
RED:UCK# %0
#
23TEXTRED:UCK
23DECIMALPLACES
23UNITGL
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
REPORT#/-CALCMPLISTFULL
MEAN
-.23
TEMPORARYVARIABLES

4
Method 14 –
H 2 Determination of the content of reducing
sugars

accessories • 6.0431.100 Pt Titrode
• Possibly additional Dosimat, e.g. 2.776.0010
Reagents • Titrant: c(Na2S2O3) = 0.1 mol/L

(see also method 13) • Sulfuric acid: w(H2SO4) = 16%
• Potassium iodide solution
• Fehling’s solution 1
• Fehling’s solution 2
H Reducing sugars
General As already mentioned under method 13, the oxidation of the reducing sugars
with Cu(II) is not stoichiometric. This is why a calibration factor obtained by us-
ing glucose standards is used. In order that approximately the same amount of
reducing sugars is always present in the beaker, different sample sizes are used
and «dilution factor» A is used for the final calculation.
Sample size table g/L invert sugar Sample size Factor A

2 15 mL 0.1333
5 6 mL 0.3333
10...20 2 mL 1
25...30 1 mL 2
Samples containing more than 30 g/L invert sugar must be appropriately di-
luted with dist. H2O before the analysis. This means that factor A will be larger
than 2.
Analysis of the sample Pipet 10.00 mL Fehling’s solution 1, 5 mL Fehling’s solution 2 and 1.0...15.0 mL
sample (see table) into a beaker. Heat the mixture and boil it for exactly 30 s.
Cool it down immediately under running water. Add 10 mL each of potassium
iodide solution, w(H2SO4) = 16% and dist. H2O and titrated with c(Na2S2O3) =
0.1 mol/L until after the first endpoint.
Calculations g/L reducing sugars = (C37 – EP1) x C02 x C31 x A

C02 = conversion factor glucose/invert sugar (1.8)
C31 = calibration factor (method 13)
C37 = mL thiosulfate solution consumed in blank determination (method 13)
A = factor for sample size (table)
Remarks • In the USA the reducing sugars content is given in g/100 mL. The above re-
sult must be divided by 10.
• We would like to point out again that the boiling period of 30 s must be ob-
served exactly and that the mixture must be cooled down immediately after-
wards.
• The content of reducing sugars after complete fermentation is between
1...2 g/L, if fermentation is stopped then it is approx. 10...30 g/L (sweet
wines may contain up to 100 g/L).
1
Method 14 –
sugars
tPA tCF
DATE TIME DATE TIME
$%45-ETH $%45-ETH
PARAMETERS # FMLA
TITRATIONPARAMETERS #
MEASPTDENSITY
MININCR±L
DOSRATEMAXMLMIN tDE
SIGNALDRIFTM6MIN '044ITRINO
EQUILIBRTIMES DATE TIME
START6/&& $%45-ETH
PAUSES DEF
H Reducing sugars
DOSELEMENTINTERNAL$ FORMULA
MEASINPUT RED:UCK# %0
#
TEMPERATURE# 23TEXTRED:UCK
STOPCONDITIONS 23DECIMALPLACES
STOP6ABS 23UNITGL
STOP6ML 23LIMITCONTROL/&&
STOP5/&&M6 SILOCALCULATIONS
STOP%0 MATCHID/&&
lLLINGRATEMAXMLMIN COMMONVARIABLES
STATISTICS REPORT
STATUS/&& REPORT#/-CALCMPLISTFULL
EVALUATION MEAN
%0# -.23
%0RECOGNITIONALL TEMPORARYVARIABLES
lX%0AT5/&&M6
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

2
Method 14 –
sugars
Result of red wine Titration curve
tFR
'044ITRINO
DATE TIME
5INIT M6$%45-ETH
SMPLSIZEG
%0MLM6
RED:UCKGL
STOP%0REACHED

H Reducing sugars
Result of white wine
tFR
'044ITRINO
DATE :EIT
5INIT M6$%45-ETH
%0MLM6
RED:UCKGL
3TOPP%0REACHED

3
Method 14 –
sugars
H Reducing sugars
4
Method 15 –
Determination of the CO2 content

accessories • 6.0258.000 Unitrode (with fixed cable) or 6.0259.100 Unitrode with 6.2104.020
electrode cable (see methods 1 and 2)
Reagents • c(NaOH) = 0.1 mol/L (see method 3)

• c(H2SO4) = 0.05 mol/L (0.1 N), e.g. Merck no. 109074 or c(HCl) = 0.1 mol/L
(0.1 N), e.g. Merck no. 109060
General Fermentation by yeasts produces large amounts of CO2, most of which, how-
ever, escapes into the atmosphere (with the exception of sparkling wines). The
amount remaining in the wine normally comes from the decarboxylation of or-
ganic acids (enzymes/carboxylases). In some cases a mixture of N2 and CO2 is
added when the wine is bottled.
J Carbon dioxide
The «fizz» of a wine is achieved with a content of 0.5...0.6 g/L CO2. A content
of 1 g/L CO2 should not be exceeded for wines (with the exception of sparkling
wines). Heavy red wines (e.g. Bordeaux) usually have a content of less than
0.5 g/L CO2.
Analysis Cool the wine to 0 °C. Place 25 mL c(NaOH) = 0.1 mol/L in a beaker and under
stirring add 10.0 mL of the cooled wine sample. In a first titration this is titrated
against c(acid) = 0.1 N to pH = 8.6 (excess NaOH). The same titrant is used to
titrate to pH = 4.0. The titrant consumption in this second titration is stored in
the Titrino, e.g. as Common Variable C35.
Pipet 10.0 mL of the same wine into a beaker and add 25 mL dist. H2O. Degas
by brief boiling, vacuum or sparging N2 – see method 4 – and titrate with c(acid)
= 0.1 N to pH = 4.0 to obtain the blank value of the sample.
Calculations The CO2 content is given in g/L (USA g/100 mL).

g/L CO2 = (C35 – EP1) x 0.44
C35 = mL titrant c(acid) = 0.1 N consumed by the cooled wine sample (pH = 8.6 to pH = 4.0)
EP1 = mL titrant c(acid) = 0.1 N consumed by the degassed wine sample
0.44 = conversion factor for CO2 (g/L)
Remarks • In «normal» wines the content is between 0.5 and 0.6 g/L CO2. These wines
should not have a content of more than 1.0 g/L CO2.
1
Method 15 –
Parameter report and calculations Parameter report and calculations

Method 15.1 Method 15.2
tPA tPA
DATE TIME DATE TIME
3%4P(-ETHA 3%4P(-ETHB
PARAMETERS PARAMETERS
3%4 3%4
%0ATP( %0ATP(
DYNAMICS/&& DYNAMICS/&&
MAXRATEMLMIN MAXRATEMLMIN
MINRATE±LMIN MINRATE±LMIN
STOPCRITDRIFT STOPCRITDRIFT
STOPDRIFT±LMIN STOPDRIFT±LMIN
3%4 3%4
J Carbon dioxide
%0ATP(/&& %0ATP(/&&
TITRATIONPARAMETERS TITRATIONPARAMETERS
TITRDIRECTIONAUTO TITRDIRECTIONAUTO
PAUSES PAUSES
START6/&& START6/&&
PAUSES PAUSES
EXTRTIMES EXTRTIMES
DOSELEMENTINTERNAL$ DOSELEMENTINTERNAL$
MEASINPUT MEASINPUT
TEMPERATURE# TEMPERATURE#
TIMEINTERVALS TIMEINTERVALS
STOPCONDITIONS STOPCONDITIONS
STOP6ABS STOP6ABS
STOP6ML STOP6ML
lLLINGRATEMAXMLMIN lLLINGRATEMAXMLMIN
STATISTICS STATISTICS
STATUS/&& STATUS/&&
PRESELECTIONS PRESELECTIONS
CONDITIONING/&& CONDITIONING/&&
REQIDENT/&& REQIDENT/&&
REQSMPLSIZE/&& REQSMPLSIZE/&&
LIMITSMPLSIZE/&& LIMITSMPLSIZE/&&
ACTIVATEPULSE/&& ACTIVATEPULSE/&&

tCF
tCF '044ITRINO
'044ITRINO DATE TIME
DATE TIME 3%4P(-ETHB
3%4P(-ETHA # FMLA
# FMLA

tDE
'044ITRINO
DATE TIME
tDE 3%4P(-ETHB
'044ITRINO DEF
DATE TIME FORMULA
3%4P(-ETHA SILOCALCULATIONS
DEF MATCHID/&&
FORMULA COMMONVARIABLES
SILOCALCULATIONS #%0
MATCHID/&& REPORT
COMMONVARIABLES REPORT#/-CALCMPLISTFULLPARAM
REPORT MEAN
REPORT#/-CALCMPLISTFULLPARAM -.23
MEAN TEMPORARYVARIABLES
-.23
TEMPORARYVARIABLES

2
Method 15 –

Method 15.3
tPA Result of red wine

'044ITRINO
DATE TIME
3%4P(-ETHC
PARAMETERS
3%4 tFR
%0ATP( '044ITRINO
MAXRATEMLMIN P(INIT 3%4P(-ETHC
MINRATE±LMIN %0ML
STOPCRITDRIFT #/GL
STOPDRIFT±LMIN
3%4
J Carbon dioxide
%0ATP(/&&
TITRATIONPARAMETERS
TITRDIRECTION
PAUSES
START6/&& Result of white wine
PAUSES
EXTRTIMES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# tFR
STOP6ABS P(INIT 3%4P(-ETHC
STOP6ML %0ML
lLLINGRATEMAXMLMIN #/GL
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tCF
'044ITRINO
DATE TIME
3%4P(-ETHC
# FMLA
#

tDE
'044ITRINO
DATE TIME
3%4P(-ETHC
DEF
FORMULA
#/# %0
#
23TEXT#/
23DECIMALPLACES
23UNITGL
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
REPORT#/-CALCMPLISTFULLPARAM
MEAN
-.23
TEMPORARYVARIABLES

3
Method 15 –
J Carbon dioxide
4
Method 16 –
Ash alkalinity
Ash The content of inorganic compounds of a wine is given by the ash. This is made
up primarily of the cations (K, Na, Ca and Mg), which are obtained after ashing
in part as sulfates or chlorides but mainly as carbonates and/or oxides. Ashing
does not determine ammonium and about 75% of the total sulfurous acid (both
are volatile). The ashing temperature must not exceed 550 °C, as above this
temperature chlorides are also volatile.
Analysis Pipet 20.0 mL sample into a platinum or quartz dish and evaporate over a water
bath or in a drying oven. In order to prevent bubble formation (particularly in
sugar-rich samples), add a drop of pure paraffin or octanol near the end of the
evaporation process. Preliminary ashing is carried out with a Bunsen burner
K Ash and ash alcalinity

flame. The sample is then placed in a muffle furnace and ashed for 30 min at
525 °C. It is then allowed to cool down in a desiccator and the ash is weighed (if
the ash still contains carbon particles then it is mixed with 5 mL dist. H2O, dried
and placed in the muffle furnace again).
The result is given in g/L to 2 decimal places.
Remarks The ash content of wines varies within relatively wide limits. White wines usually
have a lower ash content than red wines. Sherries have the largest ash content.
The ash content is normally between 1.0 and 5.0 g/L.
Method 16 – Ash alkalinity

Recommended • 6.3014.223 or 6.3026.220 Exchange Units
Reagents
• c(H2SO4) = 0.05 mol/L (0.1 N), see method 14
• c(NaOH) = 0.1 mol/L (0.1 N), see method 14
General The ash is dissolved in excess sulfuric acid and the excess acid is back-titrated
against sodium hydroxide to pH = 4.5. This determines the carbonates and
oxides, but not the chlorides and sulfates.
Analysis Slowly and carefully add 10.00 mL c(H2SO4) = 0.05 mol/L to the dish contain-
ing the cooled (and weighed) ashes. Place the dish over a hot water bath for
15 min and break up any undissolved particles with a glass rod. Cool down the
clear solution, rinse it quantitatively into a beaker with dist. H2O and titrate with
c(NaOH) = 0.1 mol/L to pH = 4.5.
Calculations The ash alkalinity is given in mval/L or mL c(titrant) = 1 mol/L per liter sample.
The two results have the same numerical value.
Ash alkalinity = C01 x (C02 – EP1)
C01 = 5 (conversion factor to 1 liter at a sample size of 20 mL and with 0.1 N acid)
C02 = 10 (mL 0.1 N acid placed in the titration vessel)
EP1 = mL titrant c(NaOH) = 0.1 mol/L up to the endpoint (pH = 4.5)
1
Method 16 –
Ash alkalinity
• Just like the ash content, the ash alkalinity also varies over a relatively wide Remarks
range. However, there is no direct relationship between these two quantities.
For example, wines that have had a lot of sulfur dioxide added to them will
have a lower ash alkalinity as a larger fraction of the cations are present as
sulfates (and not as acid-binding carbonates or oxides).
• The ash alkalinity lies normally between 10 and 20 mval/L. The lowest value
found was 5, the highest 65 mval/L.
Fig. Parameter report and calculations

Result reports, same wines as method 14
2
Method 16 –
Ash alkalinity
Parameter report and calculations Result of red wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(CINIT 3%4P(-
3%4 %0ML
%0ATP( ! ALKALMVAL,
DYNAMICS/&&
MAXRATEMLMIN

MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
3%4
%0ATP(/&&
TITRATIONPARAMETERS Result of white wine
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES tFR
MEASINPUT P(CINIT 3%4P(-
TEMPERATURE# SMPLSIZEML
TIMEINTERVALS %0ML
STOPCONDITIONS ! ALKALMVAL,
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
! ALKAL#
# %0 MVAL,
23TEXT! ALKAL
23DECIMALPLACES
23UNIT MVAL,
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

tCF
'0$4ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

3
Method 17
Determination of Ca and Mg

accessories • 6.0504.100 Ca ISE with 6.2104.020 electrode cable
• 6.0726.107 Ag/AgCl reference electrode with 6.2106.020 electrode cable
• 6.0258.000 Unitrode (with fixed cable) or 6.0259.100 Unitrode with 6.2104.020
Reagents • Titrant: c(Na2EDTA) = 0.1 mol/L, e.g. Merck no. 108431 (Titriplex III solu-
tion)

• Auxiliary complexing solution: c(acetylacetone) = 0.1 mol/L plus c(tris) =
0.2 mol/L. Weigh out 10 g acetylacetone (e.g. Merck no. 109600) and 24.2
g tris(hydroxymethyl) aminomethan (e.g. Merck no. 108386) into a 1000 mL
volumetric flask, dissolve in dist. H2O, make up to the mark with dist. H2O and
mix.
• w(HCl) = 25%, e.g. Merck no. 100312
• w(NaOH) = 32%, e.g. Merck no. 105587
General The Ca and Mg contents of wines varies between relatively wide limits. They
depend on the composition of the soil and can therefore, depending on the
location and country, vary between 40 and 300 mg/L for calcium and between
20 und 250 mg/L for magnesium. These two cations can also enter the wine as
a result of treating the must with CaSO4 or CaCO3 or by adding bentonite.
A too high Ca content can lead to unwanted precipitation which, however,
usually occurs after the wine has been bottled. Mg influences the stability of
the tartrate and the «acid taste» of the wine. The Ca content is reduced during
fermentation and the Mg/Ca ratio increases.
Both ions can be determined simultaneously by the potentiometric method
described below.
Sample preparation Pipet 25.0 mL sample into a platinum or quartz dish and evaporate in a drying
oven at 140 °C. Place the sample in a muffle furnace and ash at 600 °C until a
pure white ash is obtained. After cooling down the ash is treated carefully with 2
mL w(HCl) = 25%; the mixture is heated until everything is dissolved. The solu-
tion is transferred quantitatively into a beaker with dist. H2O.
Analysis Preneutralize the solution by adjusting its pH to 8.5 with w(NaOH) = 32%. After
the addition of 20 mL auxiliary complexing solution, titrate with c(Na2EDTA) =
0.1 mol/L until after the second endpoint (Ca ISE). EP1 corresponds to Ca and
EP2 to Mg.
Calculations The Ca and Mg contents are given in mg/L.

1 mL c(Na2EDTA) = 0.1 mol/L corresponds to 4.008 mg Ca or 2.432 mg Mg,
respectively
mg/L Ca = EP1 x C01 x C02 / C00
mg/L Mg = (EP2 – EP1) x C03 x C02 / C00
C00 = 25 (sample size in mL)
C01 = 4.008
C02 = 1000 (for 1 liter)
C03 = 2.432
1
Method 17
• In wines both calcium and magnesium are only partially present as free ions. Remarks
The remainder is bound to organic complexes (acids). In order to determine
the total content an auxiliary complexing agent is added.
• The Ca content of wines is normally 40...200 mg/L
(California up to 300 mg/L).
• The Mg content of wines is normally 70...200 mg/L
(values between 20...250 mg/L may also occur).
2
Method 17
Parameter Report and calculations of red wine
tPA tCF
DATE TIME DATE TIME
$%45- $%45-
PARAMETERS # FMLA
MEASPTDENSITY #

MININCR±L #
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# Result
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0 tFR
lLLINGRATEMAXMLMIN '0$4ITRINO
STATISTICS DATE TIME
STATUS/&& 5INIT M6$%45-
EVALUATION SMPLSIZEML
%0# %0ML M6
%0RECOGNITIONALL %0ML M6
lX%0AT5/&&M6 #AMG,
P+(.0/&& -GMG,
PRESELECTIONS STOP%0REACHED
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME Titration curve
$%45-
DEF
FORMULA
#A%0
#
##MG,
23TEXT#A
23DECIMALPLACES
23UNIT MG,
23LIMITCONTROL/&&
-G%0 %0
#
##
23TEXT-G
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

3
Method 17
Parameter report and calculations of white wine
tPA tCF
DATE TIME DATE TIME
$%45- $%45-
PARAMETERS # FMLA
MEASPTDENSITY #
MININCR±L #
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# Result
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6
STOP%0 tFR
lLLINGRATEMAXMLMIN '0$4ITRINO
STATISTICS USER
STATUS/&& DATE TIME
EVALUATION 5INIT M6$%45-
%0# SMPLSIZEML
%0RECOGNITIONALL %0ML M6
lX%0AT5/&&M6 %0ML M6
P+(.0/&& #AMG,
PRESELECTIONS -GMG,
REQIDENT/&& STOP%0REACHED
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE
'0$4ITRINO
DATE TIME Titration curve
$%45-
DEF
FORMULA
#A%0
#
##MG,
23TEXT#A
23DECIMALPLACES
23UNIT MG,
23LIMITCONTROL/&&
-G%0 %0
#
##
23TEXT-G
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

4
Method 18 –
Determination of chloride

accessories • 6.0430.100 Ag Titrode with Ag2S coating and 6.2104.020 electrode cable
Reagents • Titrant: c(AgNO3) = 0.05 mol/L, e.g. Merck no. 111718

OR: Weigh out 8.50 g AgNO3 (e.g. Merck no. 101510) into a 1000 mL volu-
metric flask, add 1 mL w(HNO3) = 65%, dissolve in dist. H2O, make up to the
mark and mix.
• Nitric acid: w(HNO3) = 65%, e.g. Merck no. 100462
General The chloride content of wine is normally 50...200 mg/L (0.05...0.2 g/L). Contents
of up to 600 mg/L have been found in wines from vineyards near the sea. In CH
and the EU wines with a content of >500 mg/L chloride must be objected to.
The USA and Au do not have any corresponding regulations.
The potentiometric titration method described below is a classic example of
how a determination method can be simplified. The USA und SA describe meth-
ods that are preceded by complicated sample preparation steps for decoloring
the wine. An additional complication is brought about by the determination
M Chloride
proper, which is a back-titration.
Analysis Pipet 50 mL sample into a beaker, treat with 1 mL w(HNO3) = 65% and 50 mL
dist. H2O and then titrate with c(AgNO3) = 0.05 mol/L until after the first end-
point.
Calculations The chloride content is given in g/L chloride and g/L NaCl.
1 mL c(AgNO3) = 0.05 mol/L corresponds to 1.773 mg Cl – or 2.922 mg NaCl
g/L Cl – = EP1 x C01 / C00
g/L NaCl = EP1 x C02 / C00
C00 = 50 (sample size in mL)
C01 = 1.773
C02 = 2.922
Remarks The normal chloride content of wine is between 50...220 mg/L. Extreme values
of 5 mg/L and 600 mg/L have also been found. There is normally no difference
between red and white wines.
1
Method 18 –
Parameter report and calculations of red wine
tPA tCF
DATE TIME DATE TIME
$%45- $%45-
PARAMETERS # FMLA
MEASPTDENSITY #
MININCR±L
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# Result
STOPCONDITIONS
STOP6ABS
STOP6ML
M Chloride
STOP5/&&M6 tFR
STOP%0 '0$4ITRINO
lLLINGRATEMAXMLMIN DATE TIME
STATISTICS 5INIT M6$%45-
STATUS/&& SMPLSIZEML
EVALUATION %0MLM6
%0# #LGL
%0RECOGNITIONALL .A#LGL
lX%0AT5/&&M6 STOP6REACHED
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&
Titration curve
tDE
'0$4ITRINO
DATE TIME
$%45-
DEF
FORMULA
#L%0
##MG,
23TEXT#L
23DECIMALPLACES
23UNIT MG,
23LIMITCONTROL/&&
.A#L%0
##
23TEXT.A#L
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

2
Method 18 –
Parameter report and calculations of white wine
tPA tCF
DATE TIME DATE TIME
$%45- $%45-
PARAMETERS # FMLA
MEASPTDENSITY #
MININCR±L
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# Result
STOPCONDITIONS
STOP6ABS
STOP6ML
M Chloride
STOP5/&&M6 tFR
STOP%0 '0$4ITRINO
EVALUATION %0MLM6
%0# #LGL
%0RECOGNITIONALL .A#LGL
lX%0AT5/&&M6 STOP6REACHED
P+(.0/&&
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&
Titration curve
tDE
'0$4ITRINO
DATE TIME
$%45-
DEF
FORMULA
#L%0
##G,
23TEXT#L
23DECIMALPLACES
23UNIT G,
23LIMITCONTROL/&&
.A#L%0
##G,
23TEXT.A#L
23DECIMALPLACES
23UNIT G,
23LIMITCONTROL/&&
SILOCALCULATION
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

3
Method 19 –
Determination of the total phosphorus content
Recommended • 6.3014.223 or 6.3026.220 Exchange Unit(s) (possibly 6.1608.040 PE bottle)

Reagents • Titrant: c(NaOH) = 0.1 mol/L (see method 3)

• Basic neutralization solution: c(NaOH) = 2 mol/L, e.g. Merck no. 109136
• Lanthanum nitrate: La(NO3)3 x 6 H2O, c = 0.1 mol/L, pH value adjusted to 4.2.
Weigh out 21.7 g La(NO3)3 x 6 H2O, e.g. Merck no. 105326, into a beaker and
dissolve in approx. 450 mL dist. H2O. Adjust the pH value with HCl or NaOH
to 4.2 and make up to 500 mL with dist. H2O.
• Acids for digestion: w(H2SO4) = 96%, e.g. Merck no. 100731 and w(HClO4) =
60%, e.g. Merck no. 100518
N Total phosphorus
General The natural phosphate content of the wine depends primarily on the properties
of the soil. The largest fraction is formed by the inorganic phosphates. A smaller
amount is organically bound and plays a role during the alcohol fermentation.
In some cases phosphate is added to slowly fermenting musts. White wine nor-
mally has a lower phosphorus content than red wine.
In order to determine the total phosphorus content the samples must first be
ashed. They are then digested with concentrated mineral acids in order to ob-
tain orthophosphates. The digestion solution is then adjusted to pH = 4.2 to ob-
tain the dihydrogen phosphate. The addition of lanthanum nitrate precipitates
lanthanum phosphate and releases an equivalent amount of nitric acid that can
be titrated with NaOH:
NaH2PO4 + La(NO3)3 = LaPO4 + 2 HNO3 + NaNO3
Sample preparation 50 mL sample is measured out into a platinum or quartz dish and evaporated
in a drying oven at 140 °C. The sample is then placed in a muffle furnace and
ashed at 600 °C until a pure white ash is obtained. After cooling down the ash
is transferred quantitatively into a Kjeldahl flask with dist. H 2O. It is then treated
with 1 mL each of HClO4 and H2SO4, heated and boiled until white acid vapors
appear. After cooling down 10 mL dist. H2O is added and it is again boiled until
the white acid vapors appear (work under a fume hood). The cooled digestion
solution is transferred to a 100 mL volumetric flask with dist. H2O, made up to
the mark and mixed.
Analysis Pipet 50 or 100 mL digestion solution into a beaker and adjust the pH to exactly
pH = 4.20 with c(NaOH) = 2 mol/L. Add 10 mL La(NO3)3 and titrate the released
acid with c(NaOH) = 0.1 mol/L to pH = 4.2 (SET mode).
Calculations
The total phosphorus content is given in mg/L PO4.
1 mL c(NaOH) = 0.1 mol/L corresponds to 4.7486 mg PO4
mg/L PO4 = EP1 x C01 x C02 / C00
EP1 = mL c(NaOH) = 0.1 mol/L up to the endpoint
C00 = sample size (absolute) in mL (25 or 50)
C01 = 4.7486
C02 = 1000 (for 1 liter)
1
Method 19 –
The normal total phosphorus content in wine is 50...750 mg/L PO4. White Remarks
wines 65...500 mg/L, red wines 150...750 mg/L. (Californian red wines up to
900 mg/L).
N Total phosphorus
2
Method 19 –
Parameter report and calculations Result of red wine
tPA tFR
DATE TIME DATE TIME
3%4P(- P(INIT 3%4P(-
3%4 %0ML
%0ATP( 0/MG,
DYNAMICS/&&
MAXRATEMLMIN
MINRATE±LMIN
STOPCRITDRIFT
STOPDRIFT±LMIN
N Total phosphorus
3%4
%0ATP(/&&
TITRATIONPARAMETERS Result of white wine
TITRDIRECTIONAUTO
PAUSES
START6/&&
PAUSES tFR
EXTRTIMES '044ITRINO
MEASINPUT P(INIT 3%4P(-
TEMPERATURE# SMPLSIZEML
TIMEINTERVALS %0ML
STOPCONDITIONS 0/MG,
STOP6ABS
STOP6ML
lLLINGRATEMAXMLMIN
STATISTICS
STATUS/&&
PRESELECTIONS
CONDITIONING/&&
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tCF
'044ITRINO
DATE TIME
3%4P(-
# FMLA
#
#

tDE
'044ITRINO
DATE TIME
3%4P(-
DEF
FORMULA
0/%0
#
##
23TEXT0/
23DECIMALPLACES
23UNITMG,
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
REPORT#/-PARAMFULLMPLISTCALC
MEAN
TEMPORARYVARIABLES

3
Method 20 –
Determination of the sulfate content

accessories • 6.0504.100 Ca ISE with 6.2104.020 electrode cable
Reagents • Titrant: c(EGTA) = 0.05 mol/L. Weigh out 19.4 g ethylene glycol-bis-(2-ami-
noethyl)-tetraacetic acid (e.g. Merck no. 108491) into a beaker and stir to
form a slurry in approx. 200 mL dist. H2O. Add w(NaOH) = 32% (method 16)
drop by drop under stirring until all the EGTA has dissolved. After cooling
down the solution is made up to 1 liter with dist. H2O and mixed.
• Precipitation reagent: c(BaCl2) = 0.05 mol/L. Weigh out 12.34 g BaCl2 x 2 H2O
(e.g. Merck no. 101719) into a 1000 mL volumetric flask, dissolve in and make
up to the mark with c(HCl) = 0.1 mol/L, then mix the solution.
• Hydrochloric acid: w(HCl) = 25% (method 16)
• Buffer solution pH = 10: Dissolve 30 g NH4Cl (e.g. Merck no. 101142) and 180 mL
w(NH3) = 25% (e.g. Merck no. 105432) in dist. H2O and make up to 1 liter with
dist. H2O.
O Sulfate
General The vines take up relatively little sulfate from the soil – the natural sulfate content
of wine is correspondingly low. The largest amount of the sulfates result from
sulfurization. In aqueous solution sulfur dioxide forms sulfite and sulfurous acid.
Sulfite is oxidized to sulfate by atmospheric oxygen:
SO2 + H2O HSO3 – + H+
HSO3 – + ½ O2 SO42– + H+
Sulfate can also enter the wine as a result of treatment with gypsum, which re-
sults in the formation of tartaric acid from potassium hydrogen tartrate and can
lower the pH:
2 KH(C4H4O6) + CaSO4 = Ca(C4H4O6) + K 2SO4 + H2(C4H4O6)
The sulfate content is calculated as g/L K 2SO4. Normally the sulfate content is
0.5...1 g/L. A content of 1...2 g/L results in the wine having a hard acidic taste.
Wine with a sulfate content of >2 g/L is regarded as being no longer marketable
(exception: red wine from the Bordeaux region).
All analysis procedures are based on the formation of insoluble barium sulfate
by barium chloride addition. In the procedure appearing below, excess barium
chloride is added to the sample and, after a reaction time has elapsed, the non-
precipitated barium is back-titrated with a complexing agent (EGTA). Under the
given titration conditions EGTA does not react with Mg ions; any Ca ions pres-
ent can be determined simultaneously.
Sample preparation As sulfurous acid would interfere (it would be determined as sulfate) it must first
be removed from the sample. Pipet 100 mL sample into a beaker and place it
on a water bath. Sparge nitrogen through the solution and add 3 mL w(HCl) =
25%. The solution is evaporated down to approx. 50 mL. After cooling down it
is transferred quantitatively to a 100 mL volumetric flask with dist. H2O, made up
to the mark and mixed.
1
Method 20 –
For a sulfate content of 0.2...1 g/L, pipet 50 mL of the prepared sample solution Analysis
into a beaker; 25 mL is used for a sulfate content of 1...2 g/L. Treat the solution
with 10.00 mL c(BaCl2) = 0.05 mol/L and allow to react for 3 min under stirring.
After the addition of 10 mL pH = 10 buffer solution, titrate with c(EGTA) = 0.05
mol/L until after the second endpoint (Ca ISE). EP1 corresponds to Ca, EP2
– EP1 to the excess barium.
The sulfate content is given in g/L K 2SO4. Calculations

1 mL c(EGTA) = 0.05 mol/L corresponds to 8.713 mg K 2SO4
g/L K 2SO4 = C01 – (EP2 – EP1) x C02 / C00
Calcium content:
1 mL c(EGTA) = 0.05 mol/L corresponds to 2.004 mg Ca
g/L Ca = EP1 x C03 / C00
C01 = 10 (mL BaCl2 solution added)
C02 = 8.713
C03 = 2.004
O Sulfate
The normal sulfate content of wine is 0.2...1.0 g/L K 2SO4. Long storage in bar- Remarks
rels increases the sulfate content. A sulfate content of 2.5 g/L has occasionally
been found in red Bordeaux wine.
2
Method 20 –
Method parameters and calculation of red wine
tPA tCF
DATE TIME DATE TIME
$%45- $%45-
PARAMETERS # FMLA
MEASPTDENSITY #
MININCR±L #
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# Result
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6 tFR
O Sulfate
STOP%0 '044ITRINO
EVALUATION %0ML M6
%0# %0ML M6
%0RECOGNITIONALL #AGL
lX%0AT5/&&M6 +3/GL
P+(.0/&& STOP%0REACHED
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE Titration curve

'044ITRINO
DATE TIME
$%45-
DEF
FORMULA
#A%0
##
23TEXT#A
23DECIMALPLACES
23UNITGL
23LIMITCONTROL/&&
+3/# %0 %0
##
23TEXT+3/
23DECIMALPLACES
23UNITGL
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

3
Method 20 –
Method parameters and calculations for white wine
tPA tCF
DATE TIME DATE TIME
$%45- $%45-
PARAMETERS # FMLA
MEASPTDENSITY #
MININCR±L #
DOSRATEMAXMLMIN
SIGNALDRIFTM6MIN
EQUILIBRTIMES
START6/&&
PAUSES
DOSELEMENTINTERNAL$
MEASINPUT
TEMPERATURE# Result
STOPCONDITIONS
STOP6ABS
STOP6ML
STOP5/&&M6 tFR
O Sulfate
STOP%0 '044ITRINO
EVALUATION %0ML M6
%0# %0ML M6
%0RECOGNITIONALL #AGL
lX%0AT5/&&M6 +3/GL
P+(.0/&& STOP%0REACHED
PRESELECTIONS
REQIDENT/&&
REQSMPLSIZE/&&
LIMITSMPLSIZE/&&
ACTIVATEPULSE/&&

tDE Titration curve

'044ITRINO
DATE TIME
$%45-
DEF
FORMULA
#A%0
##
23TEXT#A
23DECIMALPLACES
23UNITGL
23LIMITCONTROL/&&
+3/# %0 %0
##
23TEXT+3/
23DECIMALPLACES
23UNITGL
23LIMITCONTROL/&&
SILOCALCULATIONS
MATCHID/&&
COMMONVARIABLES
REPORT
MEAN
-.23
TEMPORARYVARIABLES

4
Theoretical basis for the electrodes and
measurements

As with the pH value, currentless measurements of potential differences be-
tween two electrodes (measuring electrode and reference electrode) are per-
formed with a suitable instrument (pH meter, ion meter, titrator).
The reference electrode has a constant potential (hence its name – it is used
for comparison), whereas the potential at the measuring electrode changes.
The change in potential is dependent on the concentration of the ion to be
determined and, like the pH value, obeys the Nernst equation. For positively
charged ions with a single charge the potential at 25.0 °C increases by 59.2 mV
when the concentration is increased 10-fold; for negatively charged ions with a
single charge the corresponding change in potential at 25.0 °C is –59.2 mV. For
positively charged ions with a double charge the theoretical slope is accord-
ingly 59.2 : 2 = 29.6 mV per 10-fold concentration change. This also means that
for positively charged ions the potential increases with the concentration, while
with negatively charged ions it decreases.
The electrode slope depends on the temperature.
Theoretical electrode 15.0 °C 57.2 mV

slope 1.00 (100%) as 16.0 °C 57.4 mV
a function of tempera- 17.0 °C 57.6 mV
ture
18.0 °C 57.8 mV
19.0 °C 58.0 mV
20.0 °C 58.2 mV
21.0 °C 58.4 mV
22.0 °C 58.6 mV
23.0 °C 58.8 mV
24.0 °C 59.0 mV
25.0 °C 59.2 mV
Depending on the ion that is to be determined, there are different types of ion
selective electrodes:
• Glass membrane electrodes, e.g. for pH and Na+
• Polymer membrane electrodes, e.g. for K+, Ca2+, NO3 –
• Crystal membrane electrodes, e.g. for Cl –, F–, S2–, Ag+, Cu2+
• Gas membrane electrodes, e.g. for NH3 (NH4+), CO2
ISEs respond «selectively» to the particular ion. But this is not quite true. They
may have cross sensitivities, i.e. they may also respond to other ions – this
causes interference, which must either be eliminated or reduced.
ISEs only measure ion activities. Ions are active when they are freely present as
such in the solution. The activity coefficient γ can be taken from the appropri-
ate tables. Two examples:
c(Na) = 10 –1 mol/L; γ = 0.770 a(Na) = 0.77 x 10 –1 mol/L
c(Na) = 10 mol/L; γ = 0.996 a(Na) = 0.996 x 10 –5 mol/L
–5
<gamma> not only depends on the ionic strength of the ion to be measured,
but also on the total ionic strength of the solution. In order to keep γ constant,
measurements are made at a constant (high) ionic strength. This is why ISA so-
lutions are added to the sample. ISA stands for Ionic Strength Adjuster. These
1
measurements
are solutions of salts against which the ISE has no cross sensitivity at all or only
a slight one.
Some of the ions to be determined are only present as free ions within a limited
pH range. Outside these limits they have no activity at all or only a slight activity.
Solutions for regulating the pH and ionic strength are known as TISAB solutions
(TISAB = Total Ionic Strength Adjustment Buffer). These TISAB solutions may
also contain other compounds (e.g. complexing agents for releasing the ion to
be determined or removing the interfering ions, for example Al, Ca and Fe in
fluoride determination).
The pH glass electrode is the ISE par excellence. It is very selective and can
be used for concentration measurements throughout a range of more than 14
decades. With other ISEs this is not the case. Their normal measuring range is
6 concentration decades at the most. This means that the lowest determination
level is – depending on the electrode and sample matrix – about 50...200 μg/L.
The determination of the content itself can be carried out in three different
ways:
a) Recording a calibration curve

mV measurements are carried out with standard solutions that have been
treated with ISA or TISAB in the same way as the subsequent sample solutions.
To obtain the calibration curve, U/mV is plotted on the linear scale and the con-
centration on the logarithmic scale. This calibration curve is used to determine
the content of the sample from the measured mV value.
b) «pK calibration» (analogous to pH calibration)

The procedure is similar to that for pH calibration: Standard solutions are used
whose concentrations lie in the range in which the determinations are later to be
carried out. ISA or TISAB is also added to the standard solutions. For example:
The sample contains approx. 500 mg/L potassium, M = 39.1 g/mol. This means
that the recommended range lies between 39.1 mg/L and 3910 mg/L potas-
sium. Calibration is carried out with the corresponding pK values (pK = –log c K ),
which result from the K+ concentration that is effectively present after the addi-
tion of ISA or TISAB:
3910 mg/L pK 1.592
391 mg/L pK 2.592
39.1 mg/L pK 3.592
Disadvantage: The calculation of the content with the Titrino is very compli-
cated and, depending on the content, relative errors of up to ±15% must be
expected.
c) Standard addition method

The sample is treated with ISA or TISAB and its mV value is measured. A defined
volume of the standard solution is added and the mV value is again measured.
The content of the sample can be calculated from the difference in mV and the
slope of the electrode. The advantage of this method is that it takes the sample
matrix into account (this is not the case in methods a) and b). This is why we
will use this method c) for the analyses. The activity coefficient γ is also tem-
perature-dependent. This means that the measurement of the sample with and
without the added standard must take place at the same temperature.
2
measurements

The individual electrodes:
Ammonium No interfering ions. The pH of the sample is adjusted to >11 with NaOH, as the
electrode only responds to NH3.
NH4Cl + NaOH → NaCl + NH3 + H2O
This electrode does not need to be conditioned. When not in use it is stored in
dist. H2O; if it is not to be used for a long time then it is dismantled.
Potassium An NaCl solution is used as the ISA in this case. The following ion concentra-
tions cause a variation of 10% with 10 –3 mol/L potassium
3.3 x 10 –3 mol/L NH4+
1 x 10 –4 mol/L Cs
1 x 10 –2 mol/L H+
In wine cesium (Cs) is only present in traces (if at all); pH = 2.0 is never reached
and ammonium is also never present in the same concentration as the potas-
sium.
The electrode is conditioned by immersion (30 min) in c(KCl) = 0.1 mol/L. If it is
not to be used for a long time then it is stored dry. Never leave the electrode in
the measuring solution for too long.
Sodium The Na ISE is a glass membrane electrode and, as such, also responds to acids
(pH). Measurements are made at pH >8 in order to prevent cross sensitivity/inter-
ference. Silver ions (Ag+) can cause considerable interference. In a 10 –3 mol/L Na
solution even 30 μg/L Ag is sufficient to cause a measurement error of 10%. If
wine has been treated with Ag then some K 2S must be added. This forms in-
soluble Ag2S and the interference is eliminated.
The electrode is conditioned by overnight immersion in c(NaCl) = 0.1 mol/L and
it is also stored in this solution when not in use. Before use it must be rinsed
thoroughly with dist. H2O and dabbed dry with a soft paper tissue (do not rub).
Fluoride The only interfering ion is OH –. However, as measurements are made at pH

<7.0, this interference can be neglected. On the other hand, measurements
should not be made at too low pH values as otherwise HF or H2F2 could be
formed; these are not determined. AlF3, FeF3 or CaF2 give low-bias results. For
this reason a complexing agent (e.g. EDTA) can be added to the TISAB solution.
This «releases» the fluoride from these compounds.
Before the first use, or if its response deteriorates, the electrode membrane
should be gently polished with a fat-free concentrated dishwasher and then
thoroughly rinsed with dist. H2O. When not in use the electrode is stored dry. If
small fluoride concentrations are to be determined (<1 mg/L F) then the elec-
trode should be preconditioned overnight in dist. H2O.
Further remarks Do not touch electrode membranes with your fingers. Fat deposits considerably
affect the response of the electrodes.
In order to avoid the formation of gas bubbles on the membrane surface, mea-
surements should always be carried out on degassed wine samples (vacuum
or short boiling and cooling down).
In practice the electrode slope seldom reaches a value of 1.00, but is normally
in the range 0.92...0.98. If the slope falls significantly below this range then the
electrode must be conditioned again or replaced. Be aware that incorrectly
made-up standard solutions will cause apparent variations in the slope.
3
Method 21 –

P 1 Ammonium

accessories • 6.0506.010 NH3 electrode (with fixed cable)
Reagents • w(NaOH) = 32%, e.g. Merck no. 105590

• Ammonium standard, stock solution: Weigh out 2.966 g NH4Cl, e.g. Merck
no. 101145, into a 100 mL volumetric flask, dissolve in dist. H2O, make up to
the mark and mix.
ρ(NH4+) = 10000 mg/L; 1 mL corresponds to 10 mg NH4+
• Ammonium standard for direct use: Dilute 25.0 mL stock solution with dist.
H2O to 250 mL.
ρ(NH4+) = 1000 mg/L; 1 mL corresponds to 1 mg NH4+
General The ammonium electrode is a gas membrane electrode. In alkaline solutions

gaseous ammonia (NH3) is formed from ammonium salts:
NH4+ + OH – NH3 + H2O
The NH3 diffuses through a porous PTFE membrane into an inner solution in
which a combined pH glass electrode is immersed. The ammonia entered by
diffusion alters the pH of this inner solution; the change in the pH value is pro-
portional to the logarithm of the NH4 concentration of the sample.
Ammonium is usually present in musts to a considerable extent (30...300 mg/L),
depending on the wine-growing area and fertilizers used. During fermentation
the majority of the ammonium is consumed by the yeasts (readily available and
preferred source of nitrogen). The ammonium content of wine is much lower
and lies between 0.5 and 15 mg/L. If higher contents are found (up to 50 mg/L)
this usually means that the wine has been sweetened with must before being
bottled.
Determination of the From the ammonium standard for direct use (1000 mg/L) a second standard
solution with 10 mg/L NH4 is first prepared (dilute 1:100 with dist. H2O).
electrode slope
Pipet 25.0 mL ρ(NH4) = 10 mg/L into a beaker and add a magnetic stirrer bar.
Immerse the electrode into the solution, stir and treat with 2 mL w(NaOH) =
32%. Measure the mV value, read off when the potential has steadied and re-
cord.
Rinse the electrode with dist. H2O, dab dry with a soft paper tissue and repeat
the above procedure with ρ(NH4) = 1000 mg/L.
Calculate the difference (in mV) between the two measurements and divide by
2. This gives the absolute electrode slope in mV per concentration decade. The
relative electrode slope is obtained as follows:
absolute electrode slope

relative electrode slope =
theoretical electrode slope
Analysis Pipet 25.0 mL of CO2-free sample into a beaker and add a magnetic stirrer bar.
Immerse the electrode into the solution, stir and treat with 2 mL w(NaOH) =
32%. Read off the mV value when the potential has steadied and record.
Add 0.1...1.0 mL ρ(NH4) = 1000 mg/L (note the exact volume, the volume added
should produce the optimal mV difference of approx. 15 mV), read off and record
the mV value when the potential has steadied. Calculate the mV difference.
1
Method 21 –
P 1 Ammonium
The ammonium content of wine is given as mg/L NH4+. Calculations

The ammonium content of the sample can be calculated according to the fol-
lowing equation:
where:
cx = ammonium concentration of sample in mg/L
Vst = volume of standard solution added in mL
cst = concentration of standard solution added in mg/L
V0 = sample volume in mL
V1 = sample volume + ISA or TISAB volume, both in mL
dU = difference between mV measured in sample and mV measured in sample plus standard
S = absolute electrode slope (mV per concentration decade)
The ammonium content of wine is normally 0.5...12 mg/L NH4+. Higher con- Remarks
tents (up to 50 mg/L) usually occur in wine sweetened with must. No regula-
tions exist.
2
Method 21 –

P 1 Ammonium
Calculation examples and results Calculation examples and results

of red wine of white wine
MEASURE MEASURE
tFR tFR
DATE TIME DATE TIME
-%!35- -%!35-
# M6 # M6
MANUALSTOP MANUALSTOP

MEASURE
MEASURE
tFR
'044ITRINO tFR
-%!35- DATE TIME
SMPLSIZEML -%!35-
# M6 SMPLSIZEML
MANUALSTOP # M6
MANUALSTOP

CALCULATIONEXAMPLE
CALCULATIONEXAMPLE
#X

>

#X

>

MG,

MG,
3
Method 22 –

P 2 Potassium

accessories • 6.0504.110 K ISE with 6.2104.020 electrode cable
• 6.0726.100 Ag/AgCl reference electrode, electrolyte solution c(NaCl) =
1.2 mol/L, with 6.2106.020 electrode cable
Reagents • ISA solution: c(NaCl) = 1.2 mol/L. Dissolve 17.53 g NaCl, e.g. Merck no.
106404, in dist. H2O, make up to 250 mL and mix.
• Potassium standard: ρ(K+) = 10 g/L (10 000 mg/L). Dissolve 19.073 g KCl,
e.g. Merck no. 104935, in dist. H2O, make up to 1000 mL and mix.
1 mL corresponds to 10 mg K+
General The potassium ISE is a polymer membrane electrode. Its membrane is made
of PVC and is therefore not resistant to organic solvents. However, the ethanol
content of the wine samples has no direct influence on the measurements as
the sample is diluted.
This analysis plays an important role in process control. A knowledge of the
potassium, tartrate and alcohol content together with the pH provides impor-
tant information about the stability or instability of the wine (precipitation of KH
tartrate, particularly after bottling).
Determination of the From the standard solution (10000 mg/L) a second standard solution with 100
mg/L K is first prepared (dilute 1:100 with dist. H2O).
electrode slope
Pipet 50 mL ρ(K+) = 100 mg/L into a beaker, add a magnetic stirrer bar and 5 mL
c(NaCl) = 1.2 mol/L. Immerse the electrode into the solution, stir, measure the
mV and record the mV value when the potential is constant. Rinse the electrode
with dist. H2O, dab dry with a soft paper tissue and repeat the above procedure
with ρ(K+) = 10000 mg/L.
Calculate the difference in mV between the two measurements and divide by 2.
This gives the absolute electrode slope in mV per concentration decade. The
relative electrode slope is calculated as follows:

Analysis Because of the relatively high potassium concentration the CO2-free sample is
diluted 1:10 with dist. H2O before the measurement.
Pipet 50 mL of the prepared sample solution into a beaker and treat with 5 mL
c(NaCl) = 1.2 mol/L. Add a magnetic stirrer bar, immerse the electrode and
measure the mV value under stirring. Read off and record the mV value when
the potential is constant. Add 0.1...0.5 mL ρ(K+) = 10000 mg/L (record the exact
volume, the volume added should produce the optimal mV difference of approx.
15 mV), read off and record the mV value when the potential has steadied. Cal-
culate the mV difference.
1
Method 22 –
P 2 Potassium
The potassium content of wine is given in g/L K. Calculations

The potassium content of the sample can be calculated according to the follow-
ing equation:
where:
As the sample has been
cx = potassium concentration of sample in mg/L
diluted 1:10, the primary
result must be multiplied
by 10 and divided by
1000 to obtain the potas-
sium content in g/L, as
dU = difference between mV measured in sample and mV
required.
measured in sample plus standard
The potassium content of wine is normally 0.6...1.0 g/L K. However, contents Remarks
as low as 0.28 g/L and as high as 2.04 g/L have also been found. Red wine usu-
ally has a higher potassium content than white wine.
2
Method 22 –

P 2 Potassium

MEASURE MEASURE
tFR tFR
DATE TIME DATE TIME
-%!35- -%!35-
#M6 #M6

MEASURE MEASURE
tFR tFR
DATE TIME DATE TIME
-%!35- -%!35-
#M6 #M6

CALCULATIONEXAMPLE CALCULATIONEXAMPLE
#X

>
#X

>

MG, MG,
G, G,
3
Method 23 –

P 3 Sodium

accessories • 6.0501.100 Na ISE with 6.2104.020 electrode cable
• 6.0726.100 Ag/AgCl reference electrode, internal electrolyte solution c(KCl)
= 3 mol/L, ISA solution as external electrolyte; with 6.2106.020 electrode
cable
Reagents • ISA solution: Weigh out 121 g tris(hydroxymethyl)aminomethane, e.g. Merck

no. 108387, into a plastic beaker and dissolve in approx. 500 mL dist. H2O.
Adjust the pH to approx. 9 by adding w(HNO3) = 65% and, after the solution
has cooled down, make up to 1 liter with dist. H2O (plastic bottle).
• Tris solution: c(tris) = 1 mol/L. Dissolve 121 g tris(hydroxymethyl)aminometh
ane in dist. H2O and make up to 1 liter (plastic bottle).
• Sodium standard: ρ(Na+) = 2000 mg/L. Weigh out 5.084 g NaCl, e.g. Merck
no. 106404, into a 1000 mL volumetric flask, dissolve in dist. H2O, make up to
the mark and mix.
• Conditioning solution: c(NaCl) = 0.1 mol/L. Weigh out 0.585 g NaCl into a
100 mL volumetric flask, dissolve in dist. H 2O, make up to the mark and mix.
General The Na ISE is a glass membrane electrode. As it has been developed from a
pH glass electrode it has a high cross-sensitivity to H+ ions. For this reason
measurements should always be carried out at pH values >8. c(NaCl) = 0.1
mol/L serves to precondition the Na ISE before use and to store it when it is not
being used.
Musts normally have a low sodium content (5...50 mg/L). However, in wine-
growing areas near the sea the content may be higher (up to 300 mg/L). Treat-
ment methods can introduce additional sodium into the wine (Na sulfite, hydro-
gen sulfite [bisulfite], sorbite, bentonite and by ion exchangers). The addition of
NaCl is permitted in some countries and forbidden in others. In some countries
the limit for the sodium content has also been defined and is 160 mg/L or 393
mg/L Na, the latter corresponding to 1 g/L NaCl).
Determining the From the standard solution (2000 mg/L), prepare first a second standard solu-
electrode slope tion with 20 mg/L Na (dilute 1:100 with dist. H2O in a plastic volumetric flask).
Rinse the Na ISE thoroughly before use with dist. H2O and dab it dry with a soft
paper tissue.
Add 20 mL ρ(Na+) = 20 mg/L, a magnetic stirrer bar and 20 mL ISA solution to a
plastic beaker. Immerse the electrode in the solution, stir, measure the mV value
and record it when the potential is constant. Rinse the electrode with dist. H2O,
dab dry with a soft paper tissue and repeat the above procedure with ρ(Na+) =
2000 mg/L.

1
Method 23 –
P 3 Sodium
Pipet 20.0 mL of CO2-free sample into a plastic beaker. Adjust the pH to 9.0 Analysis
with tris solution under stirring and record the volume added. If less than 20 mL
tris solution is required then make up the volume to 20 mL with ISA solution.
Immerse the electrode and measure the mV value under stirring. Record the
mV value when the potential is constant. Add 0.1...0.5 mL ρ(Na+) = 2000 mg/L
(record the exact volume, the volume added should produce the optimal mV
difference of approx. 15 mV) and record the mV value when the potential has
steadied. Calculate the mV difference.
Calculations
The sodium content of wine is given in mg/L Na.
The sodium content of the sample can be calculated according to the following
equation:
where:
cx = sodium concentration of sample in mg/L
• Sodium is ubiquitous, i.e. present everywhere. If small amounts of sodium Remarks

are to be determined, take care that the apparatus and reagents used are
scrupulously clean. This is why plastic beakers are used; sodium leaches
from glass vessels. Avoid skin contact with the sample (skin moisture con-
tains considerable amounts of sodium).
• The sodium content of wine is normally 5...80 mg/L Na. The maximum
amount present should not exceed 393 mg/L (1 g/L NaCl). The sodium con-
tent may be higher in wine-growing areas near the sea (up to 300 mg/L Na).
2
Method 23 –

P 3 Sodium

MEASURE MEASURE
tFR tFR
DATE TIME DATE TIME
-%!35- -%!35-
# M6 # M6

MEASURE MEASURE
tFR tFR
DATE TIME DATE TIME
-%!35- -%!35-
#M6 #M6

#X

>
#X

>

MG, MG,
3
Method 24 –

P 4 Fluoride
Recommended • 6.3014.213 or 6.3026.210 Exchange Unit with 6.1608.040 PP bottle

accessories • 6.0502.150 F ISE with 6.2104.020 electrode cable
Reagents • TISAB solution: Into a 1000 mL volumetric flask, weigh out 74.5 g KCl (e.g.
Merck no. 104935), 98.1 g KOOCCH3 (e.g. Merck no. 104820), 2.6 g KH2PO4
(e.g. Merck no. 104873) and 3.55 g Na 2HPO4 (e.g. Merck no. 106586), dis-
solve in dist. H2O, make up to the mark with dist. H2O and mix.
• Fluoride standard: ρ(F–) = 1000 mg/L. Weigh out 2.210 g NaF (e.g. Merck no.
106449) into a 1000 mL volumetric flask and dissolve in 100 mL TISAB solu-
tion. Make up to the mark with dist. H2O and mix. Store in a plastic bottle.
1 mL corresponds to 1.00 mg F–
General The F ISE is a crystal membrane electrode. Its sensor material is LaF3. It must
not be polished with abrasive material (e.g. aluminum oxide powder). Its use
does not normally present any problems. When not in use it is stored dry.
Fluoride is only present in wine in traces. Possible sources of fluoride are:
– Aluminum, ceramic or cement works near the vineyard
– Sugar solutions made up with fluorinated drinking water.
Detailed investigations (Europe, USA) have shown that only 4...6% of the wines
tested had a content >0.5 mg/L F.
Determining the From the standard solution (1000 mg/L) a second standard solution with
10 mg/L F is first prepared (dilute 1:100 with dist. H2O in a plastic volumetric
electrode slope flask). This solution has a limited shelf life and should be freshly prepared every
week.
Add 25 mL ρF–) = 10 mg/L, a magnetic stirrer bar and 25 mL TISAB solution
to a plastic beaker. Immerse the electrode in the solution, stir, measure the mV
value and record it when the potential is constant. Rinse the electrode with dist.
H2O, dab it dry with a soft paper tissue and repeat the above procedure with
ρ(F–) = 1000 mg/L.

Analysis Pipet 25 mL each of CO2-free sample and TISAB solution into a plastic beaker
and add a magnetic stirrer bar. Immerse the electrode and measure the mV
value under stirring. Record the mV value when the potential is constant. Add
0.1...0.5 mL ρ(F–) = 1000 mg/L and record the exact volume, which should pro-
duce the optimal mV difference of approx. 15 mV. Record the mV value when the
potential has steadied and calculate the mV difference.
1
Method 24 –
P 4 Fluoride
The fluoride content of wine is given in mg/L F. Calculations

The fluoride content of the sample can be calculated according to the following
equation:
where:
cx = fluoride concentration of sample in mg/L
• Fluoride ions can also be bound on glass surfaces to form fluorosilicates; Remarks
these cannot be determined. This is why beakers and storage vessels made
of plastic (e.g. PE or PP) are used.
• The fluoride content of wine is normally very low at 0.05...0.5 mg/L F. A
permitted maximum concentration of 0.5 mg/L (EU) or 1.0 mg/L (USA) must
not be exceeded.
2
Method 24 –

P 4 Fluoride

MEASURE MEASURE
tFR tFR
DATE TIME DATE TIME
-%!35- -%!35-
#M6 #M6

MEASURE MEASURE
tFR tFR
DATE TIME DATE TIME
-%!35- -%!35-
#M6 #M6

#X

>
#X

>

MG, MG,
3
Method 25 –

P 5 Alcohol content with the fluoride ISE
Recommended • 6.0502.150 F ISE with 6.2104.020 electrode cable

accessories • 6.0726.107 Ag/AgCl reference electrode with 6.2106.020 electrode cable
• 6.1414.010 titration vessel lid and 6.1418.250 titration vessel with thermostatic
jacket
Reagents • TISAB solution: Into a 1000 mL volumetric flask, weigh out 2.5 g Na 2EDTA x 2
H2O (e.g. Merck no. 108421), 0.22 g NaF (e.g. Merck no. 106449) and 100 g
KOOCCH3 (e.g. Merck no. 104820) and dissolve in approx. 500 mL dist. H2O.
After adding 60 mL c(NaOH) = 1 mol/L, make up to the mark with dist. H2O
and mix.
• Acetic acid solution: c(CH3COOH) = 0.05 mol/L. Place approx. 900 mL dist.
H2O into a 1000 mL volumetric flask. After adding 3.0 mL glacial acetic acid
(e.g. Merck no. 100056), make up to the mark with dist. H2O and mix.
• Alcohol standards: Prepare a standard series containing 0, 4, 8, 12, 16 and
20% ethanol by volume. (ethanol, e.g. Merck no. 159009), using six 100 mL
volumetric flasks. Fill the first volumetric flask up to the mark with acetic acid.
Add approx. 70 mL acetic acid solution to each of flasks 2 through 6. Then
add 4.00 mL ethanol to the second flask, 8.00 mL to the third flask, 12.00 mL
to the fourth flask, 16.00 mL to the fifth flask and in 20.00 mL to the sixth flask.
After the addition of ethanol, immediately make up the solutions to the mark
with acetic acid solution (20 °C), seal the flasks and mix.
General As mentioned under P «Theoretical basis for the electrodes and measure-
ments», ion selective electrodes are used to measure the activity, i.e. only the
active fraction of the particular ion can be measured. The activity coefficient γ
expresses this fraction. As we have seen, γ depends on the total ionic strength
of the solution and also on the composition of the solvent. In water-alcohol mix-
tures the activity coefficient decreases linearly as the alcohol content increases.
This situation is used to measure the alcohol content of wine. As not all wines
have the same composition, a TISAB solution of high ionic strength is added
to the sample; this solution also has a constant fluoride content. The F ISE has
been selected because it has the lowest cross-sensitivity and the natural fluo-
ride content of wine is low.
Establishing the Pipet 25 mL each of the alcohol standard and TISAB solution into the titration
beaker, add a magnetic stirrer bar, immerse the electrodes and thermostat the
calibration curve solution to 20 °C. Measure the mV value under stirring and record it when the
potential is constant. Measure the whole series of standards, starting with the
blank sample. After each measurement rinse the electrodes with dist. H2O and
dab dry with a soft paper tissue. In order to avoid loss of alcohol, make up the
mixtures just before they are to be measured.
Plot the measured values on graph paper and draw the calibration curve (mV
versus vol% alcohol). A calibration curve obtained from an Excel file is also suit-
able.
Analysis Pipet 25 mL each of the sample and TISAB solution into the titration beaker and
repeat the procedure described above for the calibration curve.
1
Method 25 –
P 5 Alcohol content with the fluoride ISE
The calibration curve is used to obtain the alcohol content of the sample from «Calculations»
its measured mV value.
• It is very important that the calibration curve and the sample measurements Remarks
are performed at the same temperature, as the activity coefficient is tempera-
ture-dependent.
• The alcohol content of wine is normally 9...13.5% alcohol by volume. Spe-
cial wines may also have a higher content (15.5% by volume).
• The «slope» of the calibration curve is approx. 2.5±0.1 mV per 4% alcohol
content (approx. 0.6 mV per 1%). The method is not suitable for exact mea-
surements and only provides information about the approximate content!
Example of a calibration
curve / Table showing
various wines with their
declared alcohol content
and that actually found.
Wine theoretical measured mV Result
White wine Fechy Cave Noe 12.0 % Vol -29.6 11.1 % Vol
red wine Feu Sacre 11.8 % Vol -30.0 11.7 % Vol
2
Index for 6.3043.003 Wine Pac
Determination Method
Alcohol 25
Ammonium 21
Ascorbic acid 12
Ash alkalinity 16
Calcium 17
Carbon dioxide (CO2) 15
Chloride 18
Fixed acidity 11
Fluoride 24
Free sulfurous acid, reference method 7
Free sulfurous acid, Ripper method 6
Magnesium 17
pH calibration 1
pH measurement 2
Phosphorus 19
Index
Potassium 22
Preparing iodide-iodate solution 1/128 mol/L 5
Preparing iodine solution 0.01 mol/L 5
Preparing NaOH 0.01 mol/L 5
Preparing NaOH 0.1 mol/L 3
Reducing sugars, calibration factor 13
Reducing sugars, determination 14
Sodium 23
Sulfate 20
Titer determination iodine solution 0.01 mol/L 5
Titer determination NaOH 0.01 mol/L 5
Titer determination NaOH 0.1 mol/L 3
Titer determination, iodide-iodate solution 1/128 mol/L 5
Titratable total acidity 4
Total phosphorus 19
Total sulfurous acid, reference method 9
Total sulfurous acid, Ripper method 8
Vitamin C 12
Volatile acidity 10
Analysis of different wine samples
Wines pH value free SO2 (titr.) total SO2 (titr.) free SO2 (dist.) total SO2 (dist.) reducing sugars
Red wine: mg/L mg/L
Santa Julia Cabernet Sauvignon Ris. '00 3.52 11.85 / (13) 63.49 / (60) 15.05 mg/L 64.98 mg/L 4.88 g/L
Syrah rouge Les Domaines Virginie '00 3.60 34.3 / ( 35) 84.43 / (82) 23.37 mg/L 90.32 mg/L 3.33 g/L
Cabert Cabernet Sauvignon Ris. '99 3.63 17.53 / (19) 65.76 / (65) 17.70 mg/L 68.10 mg/L 2.72 g/L
Saint Clair Merlot '00 3.42 25.31 / (26) 32.25 / (30) 6.49 mg/L 5.98 mg/L 2.62 g/L
Don Mendo Tinto Res. Pergamino '96 3.54 20.5 / (23) 89.96 / (92) 16.13 mg/L 62.04 mg/L 2.95 g/L
Bellingham Pinotage '00 3.67 31.17 / (30) 67.04 / (63) 11.96 mg/L 31.82 mg/L 4.16 g/L
White wine:
Santa Julia Chardonnay '01 3.52 25.46 / (24) 109.56 / ( 111) 17.71 mg/L 47.42 mg/L 4.55 g/L
Viognier Les Domaines Virginie '00 3.58 31.15 / (31) 121.14 / (122) 14.03 mg/L 9.89 mg/L 2.46 g/L
Cabert Pinot grigio '01 3.40 44.72 / (30) 120.00 / (88) 25.31 mg/L 81.05 mg/L 4.00 g/L
Saint Clair Sauvignon blanc '01 3.38 27.47 / (28) 87.18 / (87) 17.30 mg/L 73.58 mg/L 4.83 g/L
Segura Viudas Creu de Lavit '00 3.11 16.46 / (14) 75.06 / (60) 27.64 mg/L 51.06 mg/L 2.44 g/L
Bellingham Sauvignon Res. '00 3.24 29.84 / (31) 82.74 / (84) 23.32 mg/L 78.88 mg/L 2.01 g/L
( ) = SO2 Determination by wine-cellars Carreras

Method 6 Free sulfurous acid (titer determination) Method 7 Free sulfurous acid (distillation method)
Withe wine: Withe wine:

A) 50 mL 13.64 mg/L 1.064mL A) 20 mL 32.72 mg/L 2.044mL
12.46 mg/L 0.972mL 32.40 mg/L 2.024mL
B) 10 mL 21.92 mg/L 0.342mL B) 50 mL 17.24 mg/L 2.697mL

22.82 mg/L 0.356mL 17.87 mg/L 2.790mL
C) 50 mL 35.00 mg/L 2.730mL

37.02 mg/L 2.888mL
Red wine: Red wine:

A) 50 mL 25.36 mg/L 1.978mL A) 20 mL 8.13 mg/L 0.508mL
25.51 mg/L 1.990mL 7.17 mg/L 0.448mL

30.64 mg/L 0.478mL 4.56 mg/L 0.712mL
C) 50 mL 4.15 mg/L 0.324mL

5.03 mg/L 0.392mL
Sparkling wine:
A) 50mL 17.97 mg/L 1.402mL A) 20 mL 40.95 mg/L 2.558mL
17.92 mg/L 1.398mL 39.96 mg/L 2.496mL

23.72 mg/L 0.370mL 14.08 mg/L 2.198mL
C) 50 mL 8.28 mg/L 0.646mL

9.51 mg/L 0.688mL
Method 8 Total sulfurous acid (titer determination) Method 9 Total sulfurous acid (distillation method)
Withe wine: Withe wine:

A) 20 mL 41.13 mg/L 2.568mL A) 20 mL 38.90 mg/L 2.430mL calculation with C35: 71.62 mg/L
36.77 mg/L 2.296mL 40.12 mg/L 2.506mL 72.52 mg/L
B) 25 mL 10.10 mg/L 3.938mL B) 50 mL 66.55 mg/L 10.392mL 83.79 mg/L

9.99 mg/L 3.870mL 66.75 mg/L 10.008mL 84.62 mg/L
C) 10 mL 6.47 mg/L 6.474mL C) 50 mL 59.75 mg/L 9.327mL

6.43 mg/L 6.434mL 60.70 mg/L 9.478mL
Red wine: red wine:

A) 20 mL 5.60 mg/L 1.748mL A) 20 mL 44.73 mg/L 2.794mL 52.86 mg/L
5.42 mg/L 1.690mL 44.80 mg/L 2.798mL 51.97 mg/L
B) 10 mL 3.36 mg/L 0.522mL B) 50 mL 72.91 mg/L 10.930mL 77.70 mg/L

3.11 mg/L 0.486mL 73.75 mg/L 11.516mL 78.31 mg/L
C) 10 mL 5.78 mg/L 5.776mL C) 50 mL 58.61 mg/L 9.152mL

5.90 mg/L 5.896mL 58.46 mg/L 9.126mL
Sparkling wine:
A) 20 mL 130.71 mg/L 8.164mL 171.66 mg/L
125.36 mg/L 7.830mL 165.32 mg/L
B) 20 mL 50.94 mg/L 3.182mL 65.53 mg/L

50.30 mg/L 3.141mL 64.38 mg/L
C) 50 mL 120.25 mg/L 18.778mL

118.78 mg/L 18.648mL
Method overview Wine PAC 6.6043.003
Card DIR A Methode 1 A 1 pH-value - measuring electrode calibration
Methode 2 A 2 pH-value - measuring pH values
DIR B Methode 3 B 1 Titrable acidity - titrant preparation and titer determination
Methode 4 B 2 Titrable acidity - determination of titrable acidity
DIR C Methode 5 C 1 Free sulfur dioxide - titrant preparations and titer determinations
Methode 5.1 C1.1 Free sulfur dioxide - preparation and titer determination of c(NaOH) = 0.01 mol/L
Methode 5.2 C1.2 Free sulfur dioxide - preparation and titer determination of c(I 2) = 0.01 mol/L
Methode 5.3 C1.3 Free sulfur dioxide - preparation and tier determination of c(I 2) = 1/128 mol/L
Methode 6 C 2 Free sulfur dioxide - determination by the Ripper method
Methode 7 C 3 Free sulfur dioxide - determination by the Aspiration method
Methode 8 D 1 Total sulfur dioxide - determination by the Ripper method
Methode 9 D 2 Total sulfur dioxide - determination by the Aspiration method
DIR D Methode 10 E Volatile acidity - determination of volatile acidity
Methode 11 F Residual acidity
Methode 12 G Ascorbic acid (vitamin C) - determination of ascorbic acid
DIR E Methode 13 H 1 Reducing sugars - preparation of reagents and determination of the calibration factor
Methode 14 H 2 Reducing sugars - determination of reducing sugars
Methode 15 J Carbon dioxide - determination of CO 2 - content
Methode 16 K Ash and ash alkalinity - determination of ash alkalinity
DIR F Methode 17 L Calcium and Magnesium - determination of Ca and Mg
Methode 18 M Chloride - determination of chloride
Methode 19 N Total phosphorus - determination of total phosphorus content
Methode 20 O Sulphate - determination of sulphate content
DIR G Methode 21 P Direct potentiometry with the ISE - ammonium (NH 4)
Methode 22 P Direct potentiometry with the ISE - potassium (K)
Methode 23 P Direct potentiometry with the ISE - sodium (Na)
Methode 24 P Direct potentiometry with the ISE - fluoride (F)
Methode 25 P Direct potentiometry with the ISE - alcohol (ethanol)

Wine Pac: Wine P A C

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Wine Potentiometric Analysis Collection

Methods for the titrimetric / potentiometric analysis

Important symbols used in the methods

Reagents • Metrohm buffer solution pH = 4.00 (6.2307.100)

--- Example with practical values

The asymmetry potential

C) According to the USA

Presentation of the Au/RSA/USA to ±0.03 pH

tFR tFR tFR

red wine white wine sparkling wine

B Total titratable acidity

Calculation of the Titer = C00 / C01 / EP1

Method parameters and calculation Titration curve

Method parameters and calculation Titration curve

B Total titratable acidity

Method parameters and calculation Titration curve

Recommended • 6.3014.223 or 6.3026.220 Exchange Unit (possibly with 6.1608.040 PE bot-

Reagents • Titrant: c(NaOH) = 0.1 mol/L (method 3)

B Total titratable acidity

Detailed procedures A) CH, EU, Israel, RSA

meq./L = EPn x C30 x 0.1 x 1000 / C00

C00 = sample volume in mL

The determination of the total titratable acidity is important for:

Method parameters and calculation method A – red wine

B Total titratable acidity

Result method A – red wine

Method parameters and calculation method A – white wine

Result method A – white wine

Method parameters and calculation method B – red wine

B Total titratable acidity

Result method B – red wine

Method parameters and calculation method B – white wine

Result method B – white wine

Method parameters and calculation method C – red wine

B Total titratable acidity

Result method C – red wine

Method parameters and calculation method C – white wine

Result method C – white wine

Method parameters and calculation method D – red wine

B Total titratable acidity

Result method D – red wine

Method parameters and calculation method D – white wine

Result method D – white wine

Recommended • 6.3014.223 or 6.3026.220 Exchange Units

C Free sulfurous acid (SO2)

C 1.1 c(NaOH) = 0.01 mol/L

Titer = C00 / C01 / EP1 Calculation of titer

Method parameters and calculation Titration curve

C Free sulfurous acid (SO2)

Titer = C00 / C01 / EP1 Calculation of titer

Method parameters and calculation Titration curve

C Free sulfurous acid (SO2)

Method parameters and calculation Titration curve

C Free sulfurous acid (SO2)

Recommended • 6.3014.223 or 6.3026.220 Exchange Unit(s)

C Free sulfurous acid (SO2)

Detailed procedures A) Au, USA

EP1 = mL titrant up to the endpoint

C Free sulfurous acid (SO2)

C Free sulfurous acid (SO2)

C Free sulfurous acid (SO2)

C Free sulfurous acid (SO2)