Hanna Instruments HI 84533 User manual

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Instruction Manual
HI 84533
FORMOL NUMBER
MINITITRATOR
for Fruit Juices and Wines analysis
www.hannainst.com

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Dear Customer,
Thank you for choosing a Hanna Instruments product.
Please read this instruction manual carefully before using this instrument. This manual will
provide you with the necessary information for correct use of this instrument, as well as a precise
idea of its versatility.
If you need additional technical information, do not hesitate to e-mail us at [email protected]
or view our worldwide contact list at www.hannainst.com.
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.
TABLE OF CONTENTS
PRELIMINARY EXAMINATION................................................................................................. 3
GENERAL DESCRIPTION ........................................................................................................ 3
SPECIFICATIONS ................................................................................................................... 5
PRINCIPLE OF OPERATION .................................................................................................... 6
FUNCTIONAL DESCRIPTION................................................................................................... 7
TITRATOR STARTUP ............................................................................................................. 9
SETUP MENU .................................................................................................................... 10
GUIDE TO DISPLAY CODES ................................................................................................... 14
ELECTRODE PREPARATION .................................................................................................. 18
ELECTRODE CALIBRATION PROCEDURE ................................................................................. 19
pH BUFFER TEMPERATURE DEPENDENCE............................................................................ 23
DOSING PUMP INSTALLATION ............................................................................................. 24
DOSING PUMP PRIME PROCEDURE ..................................................................................... 24
PUMP CALIBRATION PROCEDURE ........................................................................................ 26
TITRATION PROCEDURE ..................................................................................................... 28
pH MEASUREMENT ............................................................................................................ 34
PC INTERFACE AND DATA TRANSFER ................................................................................... 38
TROUBLESHOOTING GUIDE ................................................................................................ 39
ELECTRODE CONDITIONING AND MAINTENANCE .................................................................. 41
ACCESSORIES ..................................................................................................................... 42
WARRANTY........................................................................................................................ 43

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PRELIMINARY EXAMINATION
Please examine this product carefully. Make sure that the instrument is not damaged. If any
damage occurred during shipment, please notify your Dealer.
Each HI 84533 minititrator is supplied complete with:
•HI 84533-70 Reagent kit for formol number in wine and fruit juices
•HI 1131B pH electrode
•HI 7662-T Temperature probe
•HI 7082 Electrode Fill Solution (30 mL)
•Two 100 mL beakers
•Tube set (aspiration tube with titrant bottle cap and dispensing tube with tip)
•Dosing Pump Valve
•5 mL Syringe (2 pcs.)
•2000 µL automatic pipette with two plastic tips
•1 mL Plastic Pipette
•Stir bar
•Power Adapter
•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.
GENERAL DESCRIPTION
The HI 84533 is a low-cost, easy to use, microprocessor-based automatic titrator that benefits from
Hanna’s years of experience as manufacturer of analytical instruments.
The instrument incorporates a simple and reliable dosing pump which ensures high dosing
reproducibility. Pump calibrations, performed with the provided Hanna reagents, assure the accuracy
of the instrument.
The instrument comes with a preprogrammed method for Formol measurements in fruit juices and
wines.
The HI 84533 performs the analysis and all the necessary calculations, with a simple and effective
user interface.

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SIGNIFICANCE OF USE
The amino-acid content in fruit juices and wines is expressed as nitrogen total assimilable determined
by formol method using an acid-base titration.
The formol number (known also as formol index) is a parameter used for evaluation of the quality
of fruit juices or wines (eg: 150-200 mg/L of assimilable N is the minimum required to avoid any
problem of stuck fermentation due to lack of nitrogen). The concentration of alpha amino nitrogen
in grapes changes as a function of maturity and crop load. The concentration increases with fruit
maturation and decreases with crop load.
Because of the importance of N on fermentation and fermentation volatiles, it is desirable to
determine the N status before fermentation.
The employment of the acid-base titration for determining the total amino-acid concentration is
possible only after neutralization of the titratable acidity of the samples (wines or fruit juices) and
blockage of the amino groups by reaction with formol base reagent. To decrease the pretitration
duration, neutralization of the titrable acidity is performed using two titrants and the pre-titration
stops at 8.2 pH endpoint value. After the reaction with formol base reagent (with pH adjusted
between 8.1 and 8.2 pH), in order to ensure it stops at set point pH value, the titration is performed
using a low concentrated titrant.
The HI 84533 is a potentiometric titrator that use a pH electrode for endpoint. The volume of the
titrant dispensing, necessary to reach the endpoint, is used to calculate the formol number. The
result is expressed in: meq/100 mL, meq/L or mg/L nitrogen total assimilable.
By simply pressing the Start key in Titrator mode, the instrument will automatically titrate the
sample to the endpoint. The current pH and temperature are continuously displayed during titration
process. The result is immediately displayed in g/L, then the instrument is ready for another
titration by pressing the Restart key.
A dedicated HELP key aids in setup, calibration, status and troubleshooting.
Other features:
•pH meter / mV meter
•Stir speed control
•Graphic mode to display the titration data
•Data can be stored using the log feature and then exported to a USB stick or
transferred to a PC using the USB connection
•Log on demand for up to 400 samples (200 for mV/pH measurements; 200 for
titration results)
•GLP feature, to view calibration data for pH electrode and pump

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SPECIFICATIONS
Titrator Range Low Range: meq/L 2.14 to 28.57 as N
meq% 0.21 to 2.85 as N
mg/L 30.0 to 400.0 as N
High Range: meq/L 21.7 to 71.4 as N
meq% 2.14 to 7.14 as N
mg/L 300 to 1000 as N
Resolution Low Range: 0.01 meq/L; 0.01 meq%; 0.1 mg/L
High Range: 0.1 meq/L; 0.01 meq%; 1 mg/L
Accuracy 3 % of reading or ± 0.1 mg/L @ 25 °C whichever is greater
Sample volume 10 mL (Low Range) / 5 mL (High Range)
Titration method Acid-base titration
Principle Endpoint titration: 8.20 pH
Pump 10 mL/min
Stirring speed 600 rpm
Log data Up to 200 samples
pH meter pH meter -2.0 to 16.0 pH / -2.00 to 16.00 pH
pH Resolution 0.1 pH / 0.01 pH
pH Accuracy ± 0.01 pH
pH Calibration 1, 2 or 3 calibration points;
4 available buffers (4.01, 7.01, 8.20, 10.01)
Temperature Manual or automatic
Compensation
mV meter mV meter -2000.0 to 2000.0 mV
mV Resolution 0.1 mV
mV Accuracy ± 1.0 mV
Log data Up to 200 samples (pH or mV)
Temperature Range -20.0 to 120.0 °C (-4.0 to 248.0 °F)
Resolution 0.1 °C
Accuracy ±0.4 °C without probe error
Electrode HI 1131B
Temperature Probe HI 7662-T
Environment 0 to 50 °C (32 to 122 °F); max 95% RH non-condensing
Power supply 12 Vdc power adapter
Dimensions 235 x 200 x 150 mm (9.2 x 7.9 x 5.9”)
Weight 1.9 kg (67.0 oz.)

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PRINCIPLE OF OPERATION
The amino-acidic nitrogen is determined by acidimetric titration after the blockage of the amino
groups using an excess of the formol (methanal) solution:
R – CH – COOH + CH2O R – CH – COO¯+ H3O+
Chemical method steps:
1. Sample (fruit juices or wines) total acidity neutralization, by titration against base strong
solution, at pH=8.2
2. Blockage of the amino-groups with formol solution (37%) adjusted to 8.2 pH.
3. Determination of the amino-acids content by second titration with base low concentration
solution until pH=8.2 (8.1-8.5).
Can see that the formol number titration is consecutive of the fruit juices and wine acidity titration.
A potentiometric acid-base titration employs a pH electrode to establish the endpoint of the titration.
The HI 84533 minititrator is designed to determine the formol number of the wines and fruit juices.
This instrument uses two titrant solutions in acidity neutralization steps (for shorting of the titration
time) and one low concentration titrant solution in the step of the formol number determination.
The pH of the formol reagent can be adjusted daily at 8.2 pH.
For precise results is important to know the sample volume and the titrant volume and concentration.
Preparation of the wine samples must follow the procedure (see section: Titration)
It is important to titrate the fresh samples of the fruit juices and wines. In order to increase the
precision of the measurement keep the fruit juices in caped vessels (avoid the prolonged air
exposure).
Formol number determination, as performed on the HI 84533 minititrator, utilizes a simple sample
preparation, a high quality dosing pump for titrant, potentiometric endpoint detector and instantaneaous
computations. To maintain the high precision of the titrator, a simple pump calibration procedure is
required. The pump calibration involves the analysis of a known volume of a known solution
(standard provided) and compensates for changes in pump dosing that may occur. This procedure
should be performed regularly.
N=CH2
reaction product with acidic
character (can be titrated with NaOH)
l l
NH2
REQUIRED REAGENTS
Code Description
HI 84533-50 Titrant for Low and High Range
HI 84533-55 Calibration Standard

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FRONT VIEW
REAR VIEW
6) Temperature probe
7) pH Electrode
8) Beaker
9) Dosing pump
10) Power switch
11) Power adapter
12) USB connector (PC interface)
13) USB connector (Storage interface)
14) Temperature connector
15) BNC electrode connector
16) Reference connector
17) Titrant bottle
18) Syringe
19) Aspiration tube
20) Dosing Pump Valve
FUNCTIONAL DESCRIPTION
OVERHEAD VIEW
1) Titrant bottle
2) Liquid Crystal Display (LCD)
3) Keypad
4) Electrode holder
5) Dispensing tube

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ESC -used to leave the current screen and to return either to the previous screen or to the
main screen. In Setup, exits a parameter without changing the value.
/-used to modify the parameters’ values, to scroll the information displayed while
viewing a help screen or to move between the options from the instrument’s Setup
CAL -used to access the Electrode and Pump calibration options
HELP -used to access/exit the instrument’s contextual help
LOG -used to save the current mV/pH reading in pH meter mode and the titration result
MENU -used to enter Setup, Recall or GLP selection menu, while instrument is in pH or
Titration mode
STIR -used to start/stop the stirrer
Note: The stirrer starts automatically during pump calibration and titration, it cannot
be stopped by pressing STIR key.
GUIDE TO INDICATORS
During the instrument’s operation information is displayed on the LCD.
Displayed icons:
KEYPAD FUNCTION
1) Current time and instrument mode information (pH meter or Titrator)
2) pH electrode condition
3) Instrument status
4) Virtual option keys
Unstable reading.Stirrer on. Pump running.
Parameter can be modified.Stirrer is not working properly.

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DOSING PUMP
The dosing pump is based on a valve that automatically moves the titrant between the titrant
bottle and syringe when filling the syringe and between the syringe and sample when
dispensing. A replaceable 5 mL plastic syringe is used to limit the amount of titrant used per test
to ensure the highest possible accuracy. Before a set of titrations, it is necessary to prime the
dosing system.
Note:Once titrations have been completed, the dosing system should be cleaned with deionized
water using the prime feature.
TITRATOR STARTUP
This is a general outline of the steps required to perform a titration. The following topics are
expanded upon in each section that follows.
•Place the instrument on a flat table. Do not place the instrument in direct sun light.
•Connect the power adapter to the instrument.
•Turn the instrument ON using the power switch from the rear panel of the instrument.
•Set up the instrument. See the “Setup Menu” section for details.
•Connect the pH electrode to the instrument.
•Connect the temperature sensor to the instrument.
•Calibrate the pH electrode.
•Connect the tubes and the valve. See the “Dosing Pump Installation” section for the
procedure.
•Remove the titrant bottle cap and replace it with the bottle cap with tubes. Place the titrant
bottle in the appropriate place on the titrator top.
•Prime the syringe. To assure high accuracy, verify there are no air bubbles in the syringe or
tubing.
•Calibrate the pump.
•Prepare the sample.
Note:Different volumes of wine are required based on the concentration. See “Titration
Procedure” for details.
•Run a titration and log sample results.
5) Stirrer and reading status
6) Main reading information
7) pH temperature compensation mode (Manual or Automatic)
8) Temperature reading

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SETUP MENU
The titrator’s setup menu may be accessed from the main screen (meter or titrator) by pressing
the MENU key, then Setup.
A list of setup parameters will be displayed with currently configured setting.
While in the setup menu it is possible to modify the instrument’s operation parameters. The
ARROW keys permit the user to scroll the setup parameters.
Press HELP to view the contextual help.
Press ESC to return to the main screen.
Concentration Unit
meq/L, meq% or mg/L.
Press the corresponding function key to change the
option.
Use Low measurement range for 30.0 - 400.0 mg/L.
Use High measurement range for 300 - 1000 mg/L.
To ensure a high accuracy, it is recommended to
recalibrate the pump after the valve, titrant or
electrode has been changed.
Use the ARROW keys to select the value.
Press Select to confirm or ESC to return to the setup
menu without saving the changes.
Calibration Timeout
Disabled or 1 to 7 days.
This option is used to set the number of days before
the pH calibration expired warning message is
displayed.
Press Modify to access the calibration timeout screen.
pH Resolution
0.1 or 0.01.
Press the displayed virtual option key to change the
option.
Range Setup

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Time
Press the Modify key to change the time and time
format.
Press Format to switch between 12 hour (am/pm)
and 24 hour mode.
Press to highlight the value to be modified. Use
the ARROW keys to change the value. Press Accept
to confirm the new value or ESC to return to the setup.
Date
Press the Modify key to change the date and date
format.
Press Format to cycle between the available date
formats.
Press to highlight the value to be modified. Use
the ARROW keys to change the value. Press Accept
to confirm the new value or ESC to return to the setup.
Key Beep
Select Enable to activate or Disable to deactivate
the Key Beep function.
If enabled, a short beep will be heard every time a
key is pressed.
°C, °F or K.
Press the virtual option key to change the option.
Temperature Unit

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LCD Contrast
This option is used to set the display’s contrast.
Press Modify to change the display’s contrast.
The default value is 8.
Use the ARROW keys or / to increase/
decrease the value.
Press Accept to confirm the value or ESC to return to
the setup menu.
LCD Backlight
Use the ARROW keys or / to increase/
decrease the backlight level.
Press Accept to confirm or ESC to return to the
setup menu.
Press Modify to change the backlight level.
The default value is 3.
Decimal Separator
This option allows the user to select the symbol
used for a decimal separator.
Error Beep
Select Enable to activate or Disable to deactivate
the Error Beep function.
If enabled, a beep will be heard when an error
condition occurs.

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Press the corresponding virtual option key to change
the language.
If the selected language cannot be loaded, the
previously selected language will be reloaded.
If no language can be loaded at startup the instrument
will work in “safe mode”. In “safe mode” all
messages are displayed in English. Tutorial and
help information are not available.
Language
Press Select to view the firmware version, language
version, mV factory calibration date and time,
temperature factory calibration date and time,
method version.
Meter Information
Tutorial
Enable or Disable the Tutorial. This helpful tool
offers additional information during calibration and
titration.
Press ESC to return to the setup menu.
pH endpoint
Use the ARROW keys to select the value.
Press Accept to confirm or ESC to return to the
setup menu without saving the changes.
Press Modify to change the pH endpoint value.
The default value is 8.3 pH.

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GUIDE TO DISPLAY CODES
Titration screen when a titration is in progress.
Titration screen display.
This screen appears when the instrument is turned
on during the initialization process.
Prime burette screen.
Prime burette screen when the dosing system is
running.
Restore Factory Settings
Press Select to restore the factory settings.
Press Yes to confirm the restore process or No to
return without restoring.
Press ESC to return to the setup menu.

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This error message appears during pump calibration
when the endpoint can not be reached and the
maximum amount of titrant is exceeded. Check
standard, electrode and/or dosing system and try
again.
The calibration was outside the acceptable limits.
Prepare a new standard and try again.
This error message appears when the pH reading
exceeds the acceptable input limits (-2.00 < pH
< 16.00).
This screen appears while pump calibration is in
progress. Press ESC or Stop key to return to the
Pump Calibration screen.
PUMP CALIBRATION MESSAGES
Pump calibration is initiated by pressing the Start
key.
This error message appears when the pump is not
working properly. Check the tubing, valve and syringe.
Press Restart to try again.
This screen appears when the titrator is in calibration
mode.
Press Pump to calibrate Pump.
Press Electrode to calibrate pH electrode.

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pH CALIBRATION MESSAGES
pH calibration mode.
When the reading has stabilized press Confirm to
accept the calibration or Clear to restore the default
calibration.
The “Wrong Buffer”message is displayed when the
pH value is outside of the acceptable range. Clean the
electrode by following the Cleaning Procedure and/or
check the buffer concentration before continuing the
pH calibration.
Press the ESC key to exit pH calibration mode.
TITRATION MESSAGES
This screen is displayed when the instrument is in
titration mode. Press Start to begin a titration, Meter
to enter pH meter mode or Prime to enter into the
prime function.
This screen appears when the stirrer is not working
properly. Check the stir bar and beaker content.
Press Restart to try again.
This error message appears when the pump is not
working properly. Check the tubing, valve and syringe.
Press Restart to try again.

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The auto pretitration is finished. Press Continue to
follow the next steps.
This error message appears when the pH value
exceed the acceptable limit for pH adjusting
procedure. Press Restart.
This message appears when the meter is refilling
the syringe to be ready for titration.
When the manual pH adjustment is finished please
continue to start the automatically fine adjustment.
This screen is displayed when the instrument is
automatically adjusting the pH to the endpoint value.
This screen is displayed when the instrument in manual
preparation phase and is waiting to adjust the pH
adding drops of HI 84533-62.
The titration result, expressed as concentration of
nitrogen in selected measurement unit, is displayed
automatically at the end of the titration. Press Restart
to start another titration or ESC to return to the main
screen.

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ELECTRODE PREPARATION
PREPARATION PROCEDURE
Remove the electrode protective cap.
DO NOT BE ALARMED IF ANY SALT DEPOSITS ARE PRESENT. This is normal with electrodes and
they will disappear when rinsed with distilled/deionized water.
During transport tiny bubbles of air may have formed inside the glass bulb. The electrode cannot
function properly under these conditions. These bubbles can be removed by "shaking down" the
electrode as you would do with a glass thermometer.
If the bulb is dry, soak the electrode in HI 70300 Storage Solution for at least one hour.
This error message appears when the pump is not
working properly. Check the tubing, valve and syringe.
Press Restart to try again.
This screen appears when the stirrer is not working
properly. Check the stir bar and beaker content.
Press Restart to try again.
This screen appears when the sample concentration
is out of range.
This error message appears when the input reading
(pH or temperature) exceeds the input limits. If the
pH or temperature values are blinking they are out
of range.

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ELECTRODE CALIBRATION PROCEDURE
It is recommended to calibrate the instrument frequently, especially if high accuracy is required.
The pH electrode should be recalibrated:
a) Whenever the pH electrode is replaced
b) At least once a week, but daily is advised
c) After testing aggressive chemicals and after the electrode is cleaned
d) When high accuracy is required
e) If the pH calibration expired warning is displayed during measurement
Every time you calibrate the instrument use fresh buffers and clean the electrode (see page 41).
PROCEDURE
A single one, two or three-point calibration can be performed, using four predefined buffers
4.01, 7.01, 8.20 and 10.01 pH. For a single point calibration any of the four buffers may be
used, 8.20 pH is recommended.
Note: The HI 84533 will not accept other pH buffers for calibration.
•Pour small quantities of selected buffer solutions into clean beakers. For accurate calibration
use two beakers for each buffer solution, the first one for rinsing the electrode and the second
one for calibration.
•Put a magnetic stir bar in the beaker that will be used for calibration.
•Remove the protective cap and rinse the electrode with some of the buffer solution to be used
for the first calibration point.
•Put the first beaker with calibration buffer in the beaker holder.
•Place the electrode holder on the top of the beaker and secure it by turning clockwise and
press STIR.
•Immerse the pH and the temperature probe approximately 2 cm (0.8”) into the buffer,
paying attention not to touch the stir bar.
To enter Electrode Calibration follow the next steps:
•Press CAL key then Electrode.
•The electrode calibration screen will be displayed.
•Press Clear to delete the previous calibration.

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Point 1 calibration
•The default buffer selected will be 7.01 if endpoint was set to 7.00 pH or else 8.20 pH will
be selected. If necessary, press the ARROW keys in order to select a different buffer value.
•The (unstable measurement) symbol will be shown on the display until the reading
becomes stable.
•When the reading is stable and close to the selected buffer, the (unstable measurement)
symbol will disappear and the Confirm key will become active.
•Press Confirm to confirm the calibration or ESC to exit calibration.
•After the first calibration point has been confirmed, press ESC to exit without performing the
second calibration point.
Point 2 calibration
•The calibrated value will be shown on the display and the second expected buffer value will
be displayed.
•Remove the electrode holder with electrodes from the top of the beaker.
•Place the second beaker with calibration buffer in the beaker holder. Rinse the electrodes in
a beaker containing the second buffer rinsing solution.
•Place the electrode holder (with electrodes) on the top of the beaker and secure it by turning
clockwise and press STIR.
•If necessary, press the ARROW keys in order to select a different buffer value.