Hanna Instruments HI84531 User manual

INSTRUCTION MANUAL
HI84531
Total Alkalinity
Mini Titrator & pH Meter
for Water Analysis

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.
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.
Dear
Customer,

3
TABLE OF CONTENTS
TABLE OF CONTENTS
1. Preliminary Examination ..................................................................................................... 4
2. Specifications..................................................................................................................... 5
3. General Description & Intended Use ..................................................................................... 7
4. Principle of Operation ......................................................................................................... 9
5. Functional Description....................................................................................................... 10
6. Titrator Startup................................................................................................................. 13
7. Setup Menu ..................................................................................................................... 14
8. Guide to Display Codes...................................................................................................... 19
8.1. Pump Calibration Messages ..................................................................................... 20
8.2. pH Calibration Messages ......................................................................................... 21
8.3. Titration Messages .................................................................................................. 22
9. Electrode Preparation........................................................................................................ 23
10. Electrode Calibration Procedure........................................................................................ 24
11. pH Buffer Temperature Dependence.................................................................................. 28
12. Dosing Pump Installation ................................................................................................ 29
13. Dosing Pump Prime Procedure ......................................................................................... 30
14. Pump Calibration Procedure............................................................................................. 32
15. Titration Procedure.......................................................................................................... 36
15.1. Tips for an Accurate Measurement .......................................................................... 39
15.2. View/Delete Titrator Recorded Data......................................................................... 39
15.3. Titrator GLP Information......................................................................................... 41
16. pH Measurement............................................................................................................ 42
16.1. View/Delete Recorded pH Data............................................................................... 43
16.2. pH Meter GLP Information ..................................................................................... 44
17. PC Interface & Data Transfer............................................................................................ 45
18. Electrode Conditioning & Maintenance.............................................................................. 46
19. Troubleshooting Guide..................................................................................................... 47
20. Accessories..................................................................................................................... 49
Certification........................................................................................................................... 50
Recommendations for Users.................................................................................................... 50
Warranty .............................................................................................................................. 50

4
PrELImINAry ExAmINATION
1. PRELIMINARY EXAMINATION
Remove the instrument and accessories from the packaging and examine it carefully. For further
assistance, please contact your local Hanna Instruments Office or email us at [email protected].
The HI84531 mini titrator is supplied with:
• HI1131B pH electrode
• HI7662-T Temperature probe
• HI84531-70 Reagent kit for titrable alkalinity in water
• HI7082 Electrode fill solution
• 100 mL beaker (2 pcs.)
• Dosing pump valve
• 5 mL syringe
• 2000 µL automatic pipette with two plastic tips
• 20 mL beaker (2 pcs.)
• Tube set (aspiration tube with titrant bottle cap and dispensing tube with tip)
• Stir bar
• Power adapter
• Instrument quality certificate
• Instruction manual
Note: Save all packing material until you are sure that the instrument works correctly. Any
damaged or defective item must be returned in its original packing material with the supplied
accessories.

5
SPECIFICATIONS
2. SPECIFICATIONS
Titrator
Range
Low Range (LR): 30.0 - 400.0 mg/L CaCO3
0.6 - 8.0 meq/L CaCO3
High Range (HR): 300 - 4000 mg/L CaCO3
6.0 - 80.0 meq/L CaCO3
Resolution LR: 0.1 mg/L / 0.1 meq/L
HR: 1 mg/L / 0.1 meq/L
Accuracy LR: ±1 mg/L or 3% of reading @ 25 °C whichever is greater
HR: ±10 mg/L or 3% of reading @ 25 °C whichever is greater
Sample volume 50 mL
Titration method Acid-base titration
Principle Endpoint titration pH 4.50 or pH 8.30
Pump speed 10 mL/min
Stirring speed 600 rpm
Log data Up to 200 samples
pH Meter
Range -2.0 to 16.0 pH / -2.00 to 16.00 pH
Resolution 0.1 pH / 0.01 pH
Accuracy ± 0.01 pH
Calibration 1, 2 or 3 calibration points;
4 available buffers (4.01, 7.01, 8.30, 10.01)
Temperature
compensation Manual or automatic
mV Meter
Range -2000.0 to 2000.0 mV
Resolution 0.1 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

6
SPECIFICATIONS
Other
Specifications
Electrode HI1131B
Temperature probe HI7662-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.)
Required Reagents
HI84531-50 Low Range Titrant
HI84531-51 High Range Titrant
HI84531-55 Calibration Standard

7
GENErAL DESCrIPTION & INTENDED USE
3. GENERAL DESCRIPTION & INTENDED USE
The HI84531 is an affordable, easy to use, microprocessor-based automatic mini titrator and
pH meter designed for the rapid and accurate analysis of Total Titratable Alkalinity in water. By
eliminating subjective factors including color indicators, errors in mathematical calculations or erratic
titrant additions from the measurement, this meter will quickly become a valuable analysis tool for
water and wastewater.
The meter benefits from Hanna Instruments’ many years of experience as a manufacturer of quality
analytical instrumentation. A clear and well-designed user interface makes the meter intuitive and
simple to use.
The meter employs a powerful and effective built-in algorithm to analyze the pH response to determine
the exact pH endpoint, then uses this to make the necessary calculations.
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 continuous displayed during titration process.
The concentration is instantaneously displayed in selected measurement units on the large dot matrix
display, 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
• 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 pH measurements; 200 for titration results)
• GLP feature, to view calibration data for pH electrode and pump
Significance of Use
Alkalinity is an important parameter for control and treatment of water (surface, drinking and
wastewater) it is indication of the waters buffering capacity or its ability to resist pH change.
Low alkalinity signifies that the water is susceptible to pH change, while high alkalinity indicates that
the water is able to resist a major change in pH.
Alkalinity is primarily a result of the carbonate (CO3
2¯), bicarbonate (HCO3¯) and hydroxide (OH¯)
concentration in water. However alkalinity concentrations include all contributions from borate,
phosphates, silicates, and other base species present.
Water samples are subject to interferences including:
• Dissolved gases that contribute to alkalinity are lost or gained during sampling, transport or
storage, these gasses can include carbon dioxide.
• Oily matter, suspend solids, precipitated and other waste matter can coat the glass electrode
causing a slow response time.

8
GENErAL DESCrIPTION & INTENDED USE
The HI84531 mini titrator uses a method based on Standard Methods for the Examination Water and
Wastewater. Standard Methods refers two types of alkalinity:
1. Strong Alkalinity or Phenolphthalein Alkalinity is typically determined by a titration to pH 8.3.
2. Total Alkalinity or Bromcresol Green Alkalinity is typically determined by a titration to pH 4.5.
The water sample is titrated until a fixed pH endpoint (4.5 or 8.3), the endpoint is determined by the
potentiometric input.

9
PrINCIPLE OF OPErATION
4. PRINCIPLE OF OPERATION
Water alkalinity determinations are based on the neutralization of all basic species contained in the
sample by titration with an acid:
OH¯ + H+H2O
In an ideal solution, the endpoint of an alkalinity titration corresponds stoichimetrically to the
complete neutralization of all the bases present. Due to the complex sample matrix, titrations are
typically performed to a fixed pH endpoint. Two types of alkalinity can be determined based on
the selected endpoint Total Alkalinity (pH 4.5) or Strong Alkalinity (pH 8.3). The endpoint can be
determined visually using a color indicator (i.e. phenolphthalein or bromocresol green), however
this endpoint can be become objective depending on the analysts. The HI84531 removes this issue
by titrating to a fixed pH endpoint (4.5 or 8.3) determined by the user. The concentration can vary
significantly with the selected pH endpoint. For precise analysis the sample size, volume of titrant
added and titrant concentration must be known.
The HI84531 Total Alkalinity Mini Titrator utilizes a simple sample preparation, a high quality dosing
pump for titrant additions, potentiometric endpoint determination and instantaneous computations.
To maintain the high accuracy of the mini titrator a simple pump calibration is required. The pump
calibration uses a known quantity of a known solution to compensate for changes in the dosing
system, this procedure should be performed regularly.

10
FUNCTIONAL DESCrIPTION
5. FUNCTIONAL DESCRIPTION
Front View
2
38
9
7
6
15
4
1. Dosing pump valve
2. Aspiration tube
3. Titrant bottle
4. Dispensing tube
5. Syringe
6. Temperature probe
7. pH electrode
8. Electrode holder
9. Beaker
Top View
1
4
65
2 3
1. Titrant bottle
2. Dispensing tube
3. Electrode holder
4. Liquid Crystal Display (LCD)
5. Functional keys
6. Keypad

11
FUNCTIONAL DESCrIPTION
Rear View
3
2
1
5
6
7
4
1. Power switch
2. USB connector (PC interface)
3. USB connector (storage interface)
4. Power adapter
5. BNC electrode connector
6. Reference electrode connector
7. Temperature probe connector
Keypad Description
The keypad contains 8 direct keys and 3 functional keys with the following functions:
Press the functional key to select the virtual option displayed above it on the LCD.
Press ESC key to leave the current screen and to return either to the previous screen or to
the main screen. In Setup menu, exits a parameter without changing the value.
Press ARROW keys to modify parameter values, scroll through help screens or move
between Setup options
Press CAL key to access the Electrode and Pump calibration options
Press HELP key to access/exit the instrument’s contextual help
Press LOG key to save the current mV/pH reading in pH meter mode and the titration result
Press MENU key to enter Setup, Recall or GLP selection menu, while instrument is in pH
or Titration mode
Press STIR key to start/stop the stirrer
Note: The stirrer starts automatically during pump calibration and titration, it cannot be stopped
by pressing STIR key.

12
FUNCTIONAL DESCrIPTION
Display Indicators
During the instrument’s operation information is displayed on the LCD.
1
2
3
4
5
6
7
8
1. Current time and instrument mode information (pH meter or Titrator)
2. pH electrode condition
3. Instrument status
4. Virtual option keys
5. Stirrer and reading status
6. Main reading information
7. pH temperature compensation mode (Manual or Automatic)
8. Temperature reading
Displayed icons:
Stirrer running (blinks when stirrer is not working properly.)
Pump running
Unstable reading
Parameter can be modified
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.

13
TITrATOr STArTUP
6. TITRATOR STARTUP
This is a general outline of the steps required to perform a titration. The following topics are expanded
upon 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.
Note: Different titrants are required based on the concentration. See PUMP CALIBRATION
PROCEDURE for details.
• Prime the syringe. To assure high accuracy, verify there are no air bubbles in the syringe or tubing.
• Calibrate the pump.
Note: Different volumes of standard are required based on the concentration. See TITRATION
PROCEDURE section for details.
• Prepare the sample.
• Run a titration and log sample results.

14
SETUP mENU
7. 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
mg/L or meq/L
Press the corresponding virtual option key to change the option.
Measurement Range
LR or HR
Use the table below to determine the appropriate range. Press the corresponding virtual option key
to change the option.
Note: Different titrant solutions are required for each range.
Alkalinity Type
Strong or Total
Use the table below to determine the appropriate range.
Press the corresponding virtual option key to change the option.

15
SETUP mENU
From your knowledge of expected concentrations, use the table below to determine which settings and
solutions are appropriate:
Measurement Range Low High
Range mg/L 30.0 - 400.0 300 - 4000
meq/L 0.6 - 8.0 6.0 - 80.0
Acidity Type Total Strong Total Strong
pH Endpoint 4.5 pH 8.3 pH 4.5 pH 8.3 pH
Minimum sample pH > 4.5 pH > 8.3 pH > 4.5 pH >8.3 pH
Calibration Timeout
Disabled or 1 to 7 days
Set the number of days before the pH calibration expired warning message is displayed.
Press Modify to access the calibration timeout screen.
Use the ARROW keys to select the value.
Press Select to confirm or ESC to return to the setup menu without saving the changes.
pH Resolution
0.1 or 0.01
Press the displayed virtual option key to change the resolution.
Temperature Unit
°C, °F or K
Press the virtual option key to change the option.

16
SETUP mENU
Time
Press the Modify key to change the 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 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.
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.

17
SETUP mENU
Decimal Separator
Select the symbol used for a decimal separator.
LCD 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
Press Modify to change the backlight level.
The default value is 3.
Use the ARROW keys or / to increase/decrease the backlight level.
Press Accept to confirm or ESC to return to the setup menu.
Language
The only available language is English.

18
SETUP mENU
Tutorial
Enable or Disable the Tutorial. This helpful tool offers additional information during calibration and
titration.
Meter Information
Press Select to view the firmware version, language version, mV factory calibration date and time,
temperature factory calibration date and time and method version.
Press ESC to return to the setup menu.
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.

19
GUIDE TO DISPLAy CODES
8. GUIDE TO DISPLAY CODES
This screen appears when the instrument is turned on during
the initialization process.
Titration screen display.
Titration screen when a titration is in progress.
Prime burette screen.
Prime burette screen when the dosing system is running.
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.

20
GUIDE TO DISPLAy CODES
8.1. PUMP CALIBRATION MESSAGES
Pump calibration is initiated by pressing the Start key.
This screen appears while pump calibration is in progress.
Press ESC or Stop key, to return to the Pump Calibration
screen.
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 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.