Hanna Instruments HI 84100 User manual

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Instruction Manual
HI 84100
FREE & TOTAL SULPHUR DIOXIDE
MINITITRATOR
for wine analysis
www.hannainst.com
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SALES AND TECHNICAL SERVICE CONTACTSSALES AND TECHNICAL SERVICE CONTACTS
SALES AND TECHNICAL SERVICE CONTACTSSALES AND TECHNICAL SERVICE CONTACTS
SALES AND TECHNICAL SERVICE CONTACTS
Australia:
Tel. [phone] • Fax [phone]
China:
Tel. [phone] • Fax [phone]
Egypt:
Tel. & Fax [phone]
Germany:
Tel. [phone] • Fax [phone]
Greece:
Tel. [phone] • Fax [phone]
Indonesia:
Tel. [phone] • Fax [phone]
Japan:
Tel. [phone] • Fax [phone]
Korea:
Tel. [phone] • Fax [phone]
Malaysia:
Tel. [phone] • Fax [phone]
Singapore:
Tel. [phone] • Fax [phone]
South Africa:
Tel. [phone] • Fax [phone]
Taiwan:
Tel. [phone] • Fax [phone]
Thailand:
Tel. [phone] • Fax [phone]
United Kingdom:
Tel. [phone] • Fax [phone]
USA:
Tel. [phone] • Fax [phone]
For e-mail contacts and a complete list of Sales and Technical offices, please see
www.hannainst.com.
MAN84100
09/05

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All rights are reserved. Reproduction in whole or in part is prohibited without the written consent
of the copyright owner, Hanna Instruments Inc., Woonsocket, Rhode Island, 02895 , USA.
Dear Customer,
Thank you for choosing a Hanna product. This manual will provide you with the necessary
information for the correct use of the instrument. Please read it carefully before using the meter. If
you need additional technical information, do not hesitate to e-mail us at [email protected].
This instrument is in compliance with directives.
TABLE OF CONTENTS
PRELIMINARY EXAMINATION................................................................................................. 3
GENERAL DESCRIPTION ........................................................................................................ 3
SPECIFICATIONS ................................................................................................................... 5
PRINCIPLE OF OPERATION .................................................................................................... 6
FUNCTIONAL DESCRIPTION................................................................................................... 7
START UP ............................................................................................................................ 9
GUIDE TO DISPLAY CODES ................................................................................................... 10
TIPS FOR AN ACCURATE MEASUREMENT ............................................................................. 12
FREE SO2MEASUREMENT PROCEDURE................................................................................ 12
TOTAL SO2MEASUREMENT PROCEDURE .............................................................................. 13
PUMP CALIBRATION PROCEDURE ........................................................................................ 15
PUMP TUBE REPLACEMENT ................................................................................................ 15
FUSE REPLACEMENT .......................................................................................................... 16
ELECTRODE CONDITIONING AND MAINTENANCE .................................................................. 16
ACCESSORIES .....................................................................................................................18
WARRANTY........................................................................................................................19
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Hanna Instruments reserves the right to modify the design, construction and appearance of its products
without advance notice.
HI 84100 is warranted for two years against defects in workmanship and materials when used
for its intended purpose and maintained according to the instructions.
This warranty is limited to repair or replacement free of charge.
Damage due to accident, misuse, tampering or lack of prescribed maintenance is not covered.
If service is required, contact your dealer. If under warranty, report the model number, date of
purchase, serial number and the nature of the failure. If the repair is not covered by the warranty,
you will be notified of the charges incurred.
If the instrument is to be returned to Hanna Instruments, first obtain a Returned Goods Authorization
Number from the Customer Service Department and then send it with shipment costs prepaid.
When shipping any instrument, make sure it is properly packaged for complete protection.
To validate your warranty, fill out and return the enclosed warranty card within 14 days from the
date of purchase.
WARRANTY
WARRANTY

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Please examine this product carefully. Make sure that the instrument is not damaged. If any
damage occured during shipment, please notify your Dealer.
Each HI 84100 minititrator is supplied complete with:
• Reagents set for 20 titrations
• Two 50 mL beakers
• Two 20 mL beakers
• Scissors
• Tubes set with cap
• ORP probe
• Stir bar
• Power cable
• One 30 mL bottle of Refill Solution
• One 1 mL syringe
• Two sachets of cleaning solution for wine deposits
• Two sachets of cleaning solution for wine stains
• Instruction manual
Note:Save all packing material until you are sure that the instrument works correctly.
Any defective item must be returned in its original packing.
PRELIMINARY EXAMINATION
The HI 84100 is a low-cost, easy to use, microprocessor-based automatic titrator that benefits
from Hanna’s years of experience as a manufacturer of analytical instruments.
It has a simple and reliable peristaltic pump that ensure high dosing repeatability. By
performing pump calibration with the provided Hanna standards, the instrument accuracy is
assured.
The instrument comes with a pre-programmed analysis method designed for Free and Total
Sulphur Dioxide measurements on wine samples. The instrument has a powerful and effective
built-in algorithm to analyze the shape of the electrode response and to determine the reaction
completion. This algorithm automatize the analysis, makes all the necessary calculations and
assures a simple and effective interface for the user.
By simply pressing the START STOP button, the instrument will automatically make the titration
up to the equivalence point. The result is immediately displayed in convenient units, then the
instrument is ready for another titration.
GENERAL DESCRIPTION
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Recommendations for Users
Before using this product, make sure that it is entirely suitable for your specific application and
for the environment in which it is used.
Operation of this instrument may cause unacceptable interferences to other electronic equipments,
this requiring the operator to take all necessary steps to correct interferences.
Any variation introduced by the user to the supplied equipment may degrade the instrument EMC
performance.
To avoid damages or burns, do not put the instrument in microwave ovens. For yours and the
instrument safety do not use or store the instrument in hazardous environments.
REAGENT SETS
HI 70300L Electrode storage solution (500 mL)
HI 70635L Cleaning solution for wine deposits (500 mL)
HI 70636L Cleaning solution for wine stains (500 mL)
HI 7082 Electrode filling solution (4 X 30 mL)
HI 84100-50 Titrant solution (100 mL)
HI 84100-51 Alkaline reagent (500 mL)
HI 84100-52 Acid reagent for Total SO2determination (500 mL)
HI 84100-53 Acid reagent for Free SO2determination (500 mL)
HI 84100-54 Stabilizer reagent (25 pcs.)
HI 84100-55 Calibration standard (500 mL)
OTHER ACCESSORIES
HI 3148B /50 ORP probe with 50 cm cable
HI 70483T Tube set with cap for titrant bottle and tip
HI 731316 Stir bar (5 pcs.)
HI 740036P Beaker 50 mL (10 pcs.)
HI 740037P Beaker 20 mL (10 pcs.)
HI 740198 Power cable
ACCESSORIES

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An important reason for adding SO2 is to avoid oxidation. When there is oxygen around, SO2itself
becomes oxidized before phenol compounds in the wine , and so acts as an oxygen scavenger. Also
SO2 suppresses the activity of enzymes that cause browning and other problems.
What is really protecting your wine is molecular SO2. When you add SO2, depending of circum-
stances, some of it immediately becomes bound. The relationship between the amount of added SO2
and the amount of SO2remaining free is complex. It is clear, however, that it is largely governed by
the total SO2content of the wine. The rate of binding decreases as the free SO2concentration
increases. The exact relationship between free and bound (total - free) SO2will vary from wine to
wine.
Below 30-60 ppm, 33% to 50% of SO2addition becomes bounded. What remains is called “free”
and it is divided in two parts. The larger, and relatively ineffective free part is “bisulphite” (HSO3-). The
smaller part of the free is the active molecular SO2. The amount of molecular SO2in your wine
depends both on the level of free SO2present as well as pH. For instance, at pH 3.2, the amount of
free SO2for 0.8 ppm molecular SO2is 22 ppm. At pH 3.5, you will need 43 ppm free - essentially
double.
Free SO2concentration (ppm) for 0.8 ppm molecular SO2:
In most situations, 0.8 ppm molecular SO2during bulk storage and at bottling will provide you with
adequate protection from oxidation and bacterial action. This includes prevention of malolactic
bacteria as well.
It is important to remember that the amount of free SO2in the wine depends on three things: how
much is added, how much was present before the addition and how much of your addition promptly
becomes bound.
The level at which molecular SO2can be detected by the human senses is about 2.0 ppm. This is also
the level which is needed for maximum protection of your wine. This is particularly true in the case
of sweet, and most notably, botrytised wines.
The Hanna HI 84100 offers the possibility to test free or total SO2in all the wines including the red
ones, that are difficult to test with manual methods because the color changes are hardly seen.
SIGNIFICANCE OF USE
pH 3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9
Free SO214 18 22 28 35 44 55 69 87 109
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STORAGE PROCEDURE
To minimize clogging and assure a quick response time, the glass bulb and the junction of the
electrode should be kept moist and not allowed to dry out.
Replace the solution in the protective cap with a few drops of HI 70300 Storage Solution or, in its
absence, Filling Solution (HI 7082). Follow the Preparation Procedure before taking measurements.
Note: NEVER STORE THE ELECTRODE IN DISTILLED OR DEIONIZED WATER.
PERIODIC MAINTENANCE
Inspect the electrode and the cable. The cable used for connection to the instrument must be
intact and there must be no points of broken insulation on the cable or cracks on the electrode
stem or bulb. Connectors must be perfectly clean and dry. If any scratches or cracks are present,
replace the electrode. Rinse off any salt deposits with water.
Probe Maintenance
Refill the reference chamber with fresh electrolyte (HI 7082). Allow the electrode to stand
upright for 1 hour. Follow the Storage Procedure above.
CLEANING PROCEDURE
• Wine deposits Soak in Hanna HI 70635 cleaning solution for 15 minutes
• Wine stains Soak in Hanna HI 70636 cleaning solution for 15 minutes
IMPORTANT: After performing any of the cleaning procedures, rinse the electrode thoroughly
with distilled water, refill the reference chamber with fresh electrolyte and soak the electrode in
HI 70300 Storage Solution for at least 1 hour before taking measurements.
For faster response, unscrew the fill hole screw during measurements.

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Range 0 to 400 ppm of SO2
Resolution 1 ppm
Accuracy 5% of reading
Method Ripper titrimetric method
Principle Equivalence point redox titration
Sample volume 50 mL
ORP Electrode HI 3148B (included)
Pump debit 0.5 mL/min
Stirring speed 1500 rpm
Environment 0 to 50 °C (32 to 122 °F); max 95% RH non-condensing
Power supply 220V/50Hz; 10VA
Dimensions 208 x 214 x 163 mm (8.2 x 8.4 x 6.4") (with beaker)
Weight 2200 g (77.6 oz.)
REQUIRED REAGENTS
Code Description Quantity/test
HI 84100-50 Titrant (for Free & Total SO2)
HI 84100-51 Alkaline Reagent (for Total SO2)5mL
HI 84100-52 Acid Reagent (for Total SO2)5mL
HI 84100-53 Acid Reagent (for Free SO2)5mL
HI 84100-54 Stabilizer (for Free & Total SO2) 1 packet
HI 84100-55 Standard (for Free & Total SO2) 50 mL
SPECIFICATIONS
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PREPARATION PROCEDURE
Remove the protective cap of the ORP electrode (HI 3148B).
DO NOT BE ALARMED IF SALT DEPOSITS ARE PRESENT. This is normal with electrodes. They will
disappear when rinsed with water.
During transport, tiny bubbles of air may form inside the glass bulb affecting proper functioning of
the electrode. These bubbles can be removed by “shaking down” the electrode as you would do
with a glass thermometer.
If the bulb and/or junction is dry, soak the electrode in HI 70300 Storage Solution for at least one hour.
If the filling solution (electrolyte) is more than 2½ cm (1”) below the fill hole, add HI 7082 3.5M
KCl Electrolyte Solution.
ELECTRODE CONDITIONING & MAINTENANCE
FUSE REPLACEMENT
To change the fuse follow next steps:
• Disconnect the power cord from the rear panel of
the instrument.
• Pull out the fuse holder located near the power cord
connector.
• Replace the fuse with a similar one.
• Push the fuse holder with the fuse in the appropriate
place.

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PRINCIPLE OF OPERATION
Determination of sulphur dioxide in wine samples is made by titration of the sulphur dioxide present
in wine with iodate. In this procedure an excess of iodine is added to the wine sample and it is
titrated with iodate.
The iodate reacts with iodide and the sulphuric acid present in the wine and produces iodine:
IO3
-+ 5I-+ 6H+= 3I2+ 3H2O
The iodine produced in the reaction above reacts then with the sulphur dioxide:
H2SO3+ I2+ H2O = H2SO4+ 2HI
For precise results it is very important to know the exact sample volume, titrant volume and
concentration.
The peristaltic pump has a good repeatability but the dosing volume depends on many factors as the
diameter of the tube or the tube stretching. To compensate for all this errors, the pump need to be
calibrated. The calibration of the pump is also needed in order to have high precision of the titrations.
The calibration procedure is in fact the analysis of a known solution. By doing this, the instrument
makes a differential analysis between the standard and the wine sample. The pump volumetric debit
and the real concentration of the titrant is compensated. Only the sample volume has to be precisely
known.
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PUMP CALIBRATION PROCEDURE
Warning: The calibration of the pump must be performed each time the pump tube, the reagent
bottle or the pH electrode is changed. It is recommended to perform the pump calibration before each
set of measurements.
• To prepare the sample for calibration, follow the
measurement procedure for Free or Total SO2
measurements by using HI 84100-55 Standard
instead of wine sample.
• After sample preparation, press the CAL PUMP button.
Std will blink on the screen.
• Press START STOP in order to start the system
calibration.
• At the end of the calibration procedure done appears
for a few seconds and then the meter automatically
returns to measurement mode.
PUMP TUBE REPLACEMENT
To remove the tube of the peristaltic pump follow next steps:
• Detach the old tube system from the reagent bottle.
• Grasp one fixing ring of the peristaltic pump tube.
• Pull the tube until it’s taken out from its location.
• Remove the other side of the tube.
To mount the new peristaltic pump tube follow next steps:
• Position one peristaltic pump fixing ring on its location.
• Stretch the tube over the peristaltic pump cylinders.
• Fix the second pump fixing ring on its location.
• Attach the tube to the reagent bottle.
Note: Purge the peristaltic pump until drops of reagent appears on the dosing tip by pressing the
PURGE button.

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FUNCTIONAL DESCRIPTION
FRONT PANELFRONT PANEL
FRONT PANELFRONT PANEL
FRONT PANEL
REAR PANELREAR PANEL
REAR PANELREAR PANEL
REAR PANEL
INSTRUMENT DESCRIPTION
1) Titrant bottle
2) Liquid Crystal Display (LCD)
3) Keypad
4) Electrode holder
5) Peristaltic pump tube
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• Add the content of one powder packet of HI 84100-54
Stabilizer into the beaker.
• Place the probe holder on the top of the beaker and
secure it by turning clockwise.
• Immerse the ORP electrode approximately 2 cm
(0.8”) into the sample to be tested while paying
attention to not touch the stir bar.
• Insert the dosing tip in the appropriate holder place
and pay attention to not be immersed into solution.
• Press the START STOP button to start the titration.
The display will show “titr” during titration, along
with stirrer and pump tags blinking on the LCD.
• At the end of the titration, the Sulphur Dioxide
concentration is displayed in ppm (mg/L).
Note: If the equivalence point is not reached or it is not
recognized because of the noisy solution, an error
message will be displayed.

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LCD DESCRIPTION
1) Stability indicator: when the pump calibration is in progress
2) Stirrer active tags
3) Calibration messages
4) Pump active tags
5) Four digit secondary display
6) “Time” tag: when the time is displayed on the secondary display
7) “ppm” tag: when the titration result is displayed on the primary display
8) Four digit and half main display
KEYPAD DESCRIPTION
1) PURGE - to start/stop purging (max purging time is 5 min)
2) CAL PUMP - to enter pump calibration mode
3) START STOP - to start/stop titration or pump calibration
4) STIR - to start/stop the stirrer while in measurement or purging mode
6) ORP Electrode
7) Beaker
8) BNC electrode connector
9) Fuse
10) Power switch
11) Power cable connector
12) Peristaltic pump
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• Immerse the ORP electrode approximately 2 cm
(0.8”) into the sample to be tested while paying
attention to not touch the stir bar.
• Insert the dosing tip in the appropriate holder place
and pay attention to not be immersed into solution.
• Press the START STOP button to start the titration.
The display will show “titr” during titration, along
with stirrer and pump tags blinking on the LCD.
• At the end of the titration, the Sulphur Dioxide
concentration is displayed in mg/L (ppm).
Note: If the equivalence point is not reached or it is not
recognized because of the noisy solution, an error
message will be displayed.
• Fill the 50 mL beaker up to the 50 mL mark with
the wine sample, place the stir bar into the beaker
and put the beaker in the appropriate place on the
minititrator top.
• Fill the 20 mL beaker up to the 5 mL mark with the
HI 84100-51 Alkaline Reagent and add the content
to the 50 mL beaker.
• Swirl the beaker and wait for 15 minutes.
• Fill the 20 mL beaker up to the 5 mL mark with the
HI 84100-52 Acid Reagent and add the content to
the 50 mL beaker.
TOTAL SO2MEASUREMENT PROCEDURE

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START UP
• Place the instrument on a flat table. Do not place the instrument on direct sun light.
• Connect the titrator to mains socket with ground connection and the correct voltage and
frequency. See the label on the instrument rear for this.
• Place the peristaltic pump tube on the pump. See the Pump Tube Replacement section for the
procedure.
• Remove the reagent bottle cap and place the bottle cap of the tubes set. Place the reagent
bottle in the appropriate place on the titrator top.
• Connect the tubes with the peristaltic pump (inlet tube is connected with the reagent bottle,
outlet tube is connected with the dosing tip).
• Turn the instrument ON using the power switch from the rear panel of the instrument and
wait until it displays dashes.
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The instructions listed below should be carefully followed during testing to ensure best accuracy.
• Purge the peristaltic pump to have fresh titrant when starting a new analysis or calibration.
• Calibrate the peristaltic pump before performing an analysis.
• Analyze the wine immediately after the sample is obtained.
• Clean the electrode with the HI 700635 or HI 700636 cleaning solution, specially made for
wine industry, if it was unused for a long time.
TIPS FOR AN ACCURATE MEASUREMENT
• Fill the 50 mL beaker up to the 50 mL mark with
the wine sample, place the stir bar into the beaker
and put the beaker in the appropriate place on the
minititrator top.
• Fill the 20 mL beaker up to the 5 mL mark with the
HI 84100-53 Acid Reagent and add the content to
the 50 mL beaker.
• Add the content of one powder packet of HI 84100-54
Stabilizer into the beaker.
• Place the probe holder on the top of the beaker and
secure it by turning clockwise.
FREE SO2MEASUREMENT PROCEDURE
Warning: Make sure the pump was calibrated before performing sulphur dioxide wine sample
analysis.

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GUIDE TO DISPLAY CODES
Main screen display with stirrer active.
Main screen display.
This prompt appears for a few seconds each time the instrument
is turned ON.
This screen appears each time the meter enters pump calibration
mode. The meter is ready to start pump calibration by pressing
the START STOP button.
This screen appears while pump calibration is in progress. Pressing
CAL PUMP or START STOP button, the minititrator returns to the
main screen.
This prompt appears for a few seconds before returning to the
main screen, when pump calibration is done.
Purging mode message.
PUMP CALIBRATION MESSAGES
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This error message appears when the sample concentration exceeds
400 ppm.
The used standard solution is wrong.
This error message appears when the input readings (mV) exceed
the input limits (
0÷ 1000mV).
This screen appears each time the minititrator enters TITRATION
mode. Press the START STOP button in order to stop the titration and
return to the main screen.
TITRATION MESSAGES
The titration result, expressed as concentration of sulphur dioxide in
ppm(mg/L), is displayed at the end of the titration process. Press the
START STOP button to return to the main screen.
This error message appears when the input reading exceeds the
input limits ( 0÷ 1000mV).
This screen appears when the sample concentration exceeds 400 ppm.