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450 pH/ion Meter

Instruction Manual
This manual contains complete instructions for setting up and using
the 450 pH/ion meter. Applications information is also available.
The information contained in this manual was correct at the time of
going to print. However, we continue to improve products and reserve
the right to change specifications, equipment and maintenance
procedures at any time.
This manual is copyrighted, and all rights are reserved. No part of
this manual may be reproduced by any means or in any form without
prior consent in writing.
The power supply unit is classed as IEC Class II equipment
(equipment providing an adequate degree of protection against
electric shocks, in which additional safety precautions, for example,
double or reinforced insulation, are included). The 450 is intended for
use by persons knowledgeable in safe laboratory practices. If the 450
is not used in accordance with these instructions for use, the
protection provided by the equipment may be impaired.
The 450 is suitable for direct current only.
This equipment generates, uses and can radiate radio frequency
energy and if not installed and used in accordance with the
instruction manual, may cause interference with radio
communications. It has been tested and found to comply with the
limits for a Class A computing device pursuant to Subpart J of
Part 15 of FCC Rules, which are designed to provide reasonable
protection against such interference when operated in a commercial
environment. Operation of this equipment in a residential area is
likely to cause interference in which case the user at his own expense
will be required to take whatever measures may be required to
correct the interference.
There are no user replaceable parts in the 450 or power supply unit.
Do not remove the covers.

109120-1 Rev. A, 11/96 1


Contents

1 Set Up
1.1 Unpacking and Installation ................................................ 5
1.2 Input and Output Connections ........................................... 6
1.3 Display and Controls ......................................................... 7
1.4 Programming Menu Overview ........................................... 8

2 Operation
2.1 Calibrating a pH Electrode .............................................. 10
2.1.1 pH Measurements ........................................................... 11
2.2 mV Measurements .......................................................... 11
2.2.1 Absolute mV .................................................................... 11
2.2.2 Relative mV ..................................................................... 12
2.3 Calibrating an Ion Selective Electrode ............................ 12
2.3.1 Concentration Measurements ......................................... 13
2.4 Automatic Endpoint (Auto Read) ..................................... 14
2.5 Temperature Measurements ........................................... 15
2.6 Karl Fischer Titrations ..................................................... 16
2.7 Chart Recorder ................................................................ 16
2.8 Interfacing via the RS232 Output .................................... 17

3 Meter Programming
3.1 Calibration Menu ............................................................. 20
3.1.1 Calibration Point Setting .................................................. 20
3.1.2 Last Calibration Recall .................................................... 21
3.1.3 Isopotential Point Setting (pH) ........................................ 21
3.2 Display Menu ................................................................... 22
3.2.1 Channels to Display ......................................................... 22
3.2.2 Units for Concentration to Display ................................... 22
3.2.3 Resolution for pH to Display ............................................ 23

2 109120-1 Rev. A, 11/96


Contents (cont)

3 Meter Programming (cont)

3.3 System Menu ................................................................... 24


3.3.1 Time and Date ................................................................. 24
3.3.2 Language ......................................................................... 24
3.3.3 Baud Rate ........................................................................ 25
3.3.4 Beeper on/off ................................................................... 25
3.4 Temperature Menu .......................................................... 26
3.4.1 Temperature Probe Selection ......................................... 26
3.4.2 Manual Temperature Set ................................................. 26
3.5 Limits Menu ..................................................................... 27
3.5.1 Alarm Visual and Audible On/Off .................................... 27
3.5.2 Set High/Low Limits for pH .............................................. 27
3.5.3 Set High/Low Limits for Temperature .............................. 28
3.6 Datalog Menu .................................................................. 29
3.6.1 Datalogger On/Off ........................................................... 29
3.6.2 Timer Setting ................................................................... 29
3.6.3 Recall Logged Data ......................................................... 30
3.6.4 Clearing Logged Data ..................................................... 31
3.7 GLP (Good Laboratory Practice) Menu ........................... 32
3.7.1 GLP On/Off ...................................................................... 32
3.7.2 Calibration Alarm Setting ................................................. 32
3.7.3 Entering an ID Number .................................................... 33
3.8 Diagnostics Menu ............................................................ 34
3.8.1 Meter Self Test ................................................................ 34
3.8.2 Meter Reset ..................................................................... 35

109120-1 Rev. A, 11/96 3


Contents (cont)

4 Support Information
4.1 Basic Theory .................................................................... 36
4.2 Operating Hints ................................................................ 37
4.3 Maintenance .................................................................... 38
4.3.1 Meter Maintenance .......................................................... 38
4.3.2 Electrode Maintenance .................................................... 38
4.4 Problem Solving .............................................................. 39
4.4.1 Meter Test ....................................................................... 39
4.4.2 Meter Error Codes ........................................................... 40
4.4.3 Electrode Problem Solving .............................................. 41
4.5 Meter Specifications ........................................................ 43

Consumables and Accessories ............................... inside rear cover

Warranty .................................................................. inside rear cover

4 109120-1 Rev. A, 11/96


1.1 Unpacking and Installation

1. The main carton will contain the following:

1
Meter with shorting (test) clips in the input sockets
Meter Dust Cover
Power Supply
This Instruction Manual
Memo Cards, English, French, German, Italian,
Spanish
Guide to ISE Measurements
Warranty Card
Calibration Certificate

2. If you ordered the meter with an electrode, electrode arm


and accessories, the top tray of the main carton will
contain these items. Refer to the accessories packing sheet
for a list of the additional components.

3. Attach the electrode arm to the pH/ion meter:


a. The electrode arm can be attached to the left or right-
hand side. Using the screwdriver supplied remove the
appropriate end cap from the pH/ion meter.
b. Slide the arm base into the recess and tighten the fixing
screw. Replace the end cap.
c. Fit the electrode arm onto the post. Adjust the tension
screw as required.

electrode arm

arm base
end cap

screwdriver
fixing screw tension screw

4. Fill in and return the warranty card. For your record make
a note of the serial number, date of purchase and supplier
on the inside front cover of this manual.

109120-1 Rev. A, 11/96 5


1.2 Input and Output Connections
DC - power KF - polarizing ATC - ATC (automatic temperature
supply unit current source compensation) probe socket

1
socket for Karl Fischer
titrations pH - combination or pH electrode
sockets, Channel A & B

A B

DATA - data REC - recorder REF - PT - PT1000


output socket, output socket, reference (automatic
see Section 2.8 see Section 2.7 electrode temperature
for interfacing for details sockets, compensation)
details Channel A & B probe sockets

1. Disconnect the shorting clips from the pH sockets and


retain by clipping over the socket. If you are using two
sensing electrodes connect them to Channel A and B. If you
are using one electrode, connect it to Channel A.

2. Connect the reference electrode(s), if using, to the REF


socket(s).

3. If you are using an ATC probe connect it to the ATC socket.


If you are using a PT1000 probe connect it to the PT
sockets.

4. Connect the power supply unit to the DC socket.

5. When the 450 is powered up it carries out a display self


test.

6 109120-1 Rev. A, 11/96


1.3 Display and Controls

1
mode Selects pH, mV, relative mV or concentration mode (for
Channel A or Channel B).

prog Accesses software menu from current mode. Exits


software␣ menu one step at a time.

auto
read Selects automatic endpoint detection.

on/off Turns the display off, and places the meter in standby
mode. Wakes the meter up.

cal Starts a calibration sequence in pH, relative mV and


concentration modes.
Starts sample measurement in all modes. Press again to
read freeze display in manual endpoint mode. Starts and stops
timed data logging. Returns to measurement from
software␣ menu.

enter Selects options in software menu, and enters data or


selection.

arrows Used to move around software menu.

numeric Data entry keys, to set calibration buffers, date/time,


keypad high/low limits etc. Can also be used to move around
software menu quickly.

109120-1 Rev. A, 11/96 7


1

8
The 450 uses a menu system of software for the set up functions. There are eight main menus, these
are: calibration, display, system, temp, limits, datalog, GLP, diagnostics. This chart shows the eight
main menus and their sub routines.
prog

1 2 3 4 5 6 7 8

calibration display system temp limits datalog GLP diagnostics

1 cal points channel time/date ATC type alarm on/off on/off self test

2 last cal conc units language manual set limits timer cal alarm reset

3 iso pH resolution baud temp recall data ID no.

beeper clear data


4
1.4 Programming Menu Overview

Use the arrow keys to move around the software menu.

<
The numeric keypad can also be used as quick access keys. For example, to
enter change the display resolution to X.XX, press prog then 2 (to access menu 2),
<
< 3 (to access sub routine 3), 2 (to select option 2).

<
This is useful when operating the 450 remotely from a PC, see Section 2.8.

109120-1 Rev. A, 11/96


1.4 Programming Menu Overview (cont)

To access the menus:


press prog the display shows three menus at a time (if you are

1
using both measurement channels (A and B), you have
to select which channel you want to set up).
< calibration display system >
<
Press
< and to move round the menus.You can move
either way, and the menu wraps round at
each end. Each time you press an arrow key
the next menu appears, e.g. press
<
< display system temp >

To access the menu sub routines, press enter or when

<
your required menu is highlighted,

e.g. to access the display menu sub routine press enter

< display system temp >


channel
conc units Use to move down through the
<

pH resolution sub routines.

To access your chosen sub routine press enter or


<
To choose from options displayed use and then
<
<

press enter
Before you can enter or change a value the value must be
flashing, for example: cal 1 = 7.000
Press enter Change the flashing value using the keypad, then
press enter again.

Press read to return directly to measurement.

109120-1 Rev. A, 11/96 9


2.1 Calibrating a pH Electrode

If you are using an ATC probe (or an electrode incorporating


ATC), temperature is being measured and the buffer value is
being corrected for temperature (see Section 2.5). If you are not
using an ATC in the system, the temperature can be entered
manually (see Section 3.4.2).

If you have the 'auto read' feature (see Section 2.4) turned on,
the meter will automatically endpoint when the reading is stable.
To manually endpoint and freeze the display press
read
1 point calibration
Place the tip of the electrode in the first buffer and press cal

If you are displaying both channel A and B, select the one you
are calibrating and press enter

2 The calibration buffer screen will display. Five calibration


buffers are shown on the display. If you want to use other
buffers, you will need to enter the values (see Section 3.1.1). At
the measurement endpoint a tick (✔) will appear next to the
calibration buffer and the electrode offset will display (in mV).
Rinse the tip of the electrode with distilled or deionized water
and goto pH Measurements (Section 2.1.1) or 2 point calibration.

2 point calibration
Place the tip of the electrode in the second buffer and press cal
At the measurement endpoint a tick (✔) will show next to the
buffer and the electrode slope will display.
Rinse the tip of the electrode with distilled or deionized water
and goto pH Measurements (Section 2.1.1) or 3 point calibration.

10 109120-1 Rev. A, 11/96


2.1 Calibrating a pH Electrode (cont)

3, 4 and 5 point calibration


Repeat above procedure using the third, fourth and fifth buffers.
NOTES The five buffers can be selected for calibration in any
order.
Use and to select the buffer you want to
<
<
use for the calibration and press cal

2.1.1 pH Measurements

NOTE Good laboratory practice dictates that electrodes


should be calibrated at least daily.
Place the tip of the electrode in the sample and press read to
start the measurement. The decimal point will be
flashing whenever the electrode is reading.

2
If you are using the 'auto read' function the display freezes when
a stable endpoint is reached (see Section 2.4). To manually freeze

the display when the reading is stable, press read

2.2 mV Measurements
The millivolt capability of pH meters can be used to determine the
actual slope of pH electrodes but is most frequently used for doing
potentiometric readings or titrations with Platinum Oxidation-
Reduction electrodes.

2.2.1 Absolute mV

Press mode until mV shows at the top of the display.

Put the tip of the electrode in the sample and press read The
meter will display absolute millivolts.

When the reading is stable, press read to freeze the display (or
use 'auto read', see Section 2.4).

109120-1 Rev. A, 11/96 11


2.2 mV Measurements (cont)

2.2.2 Relative mV
Press mode until Rel mV shows at the top of the display.

Put the tip of the electrode in the reference solution and press
cal The meter will be displaying absolute millivolts.

When the reading is stable, press read to freeze the display (or
use 'auto read', see Section 2.4).

The display will update to a relative mV value 0.0 mV.

Put electrode in test sample and press read (or use


'auto read'). The meter will show the change in mV from 0.0 mV.

2.3 Calibrating an Ion Selective Electrode

2 If you have the 'auto read' feature (see Section 2.4) turned on,
the meter will automatically endpoint when the reading is stable.

To manually endpoint and freeze the display, press read

To calibrate an electrode:
Press cal If you are using both measurement channels (A
and B), select the one you want to calibrate
using and then␣ press enter
<
<

Five calibration standards are shown on the display. If you want


to use other standards, you will need to enter the values (see
Section 3.1.1).

1 point calibration
Place the tip of the electrode in the first standard. At the
measurement endpoint a tick (✔) appears.

The electrode offset is displayed.

To return to sample measurement press read

12 109120-1 Rev. A, 11/96


2.3 Calibrating an Ion Selective Electrode (cont)

2 point calibration
To continue with a 2 point calibration:
Place the tip of the electrode in the second standard and
press cal

When the display freezes the electrode slope value will be


displayed.
To return to sample measurement press read
3, 4 and 5 point calibration
Repeat the procedure using the third, fourth and fifth calibration
standard.
NOTES The standard set for the first calibration standard is
the isopotential point.
The five standards can be selected for calibration in

2
any order.
Use and to select the standard you want to
<
<

use for the calibration and press cal

2.3.1 Concentration Measurements

We recommend regular calibration before sample measurements


(see Section 2.3). To measure concentration: Place the tip of the

electrode(s) in the sample and press read

The display will show the concentration of the sample. The units
can be changed (see Section 3.2.2). If you are using a
temperature probe, temperature of the sample will be displayed.
If you are using 'Auto' endpoint the display will freeze
automatically (see Section 2.4). To endpoint manually

press read

109120-1 Rev. A, 11/96 13


2.4 Automatic Endpoint (Auto Read)

The 'auto read' function checks the electrode output for stability
and automatically freezes the display when the reading appears
stable. It can be used during calibration and routine
measurements.
auto
Turn auto endpoint on by pressing read

The auto endpoint indicator A will appear at the top of the


meter display. While the meter is reading, the decimal will flash.
When the endpoint is reached, it will stop flashing.

To start another reading press read

auto
To cancel auto endpoint press read again.

14 109120-1 Rev. A, 11/96


2.5 Temperature Measurements

To measure temperature you must be using an ATC probe or the


3-in-1 Combination electrode which includes an ATC probe. If
you do not have an ATC probe the temperature will default to
25°C or the temperature that you have set manually (see Section
3.4.2). If an ATC is in use the display will show ATC or PT1000
(see Section 3.4.1). If not the display will show MTC and 25°C (or
the manually set temperature).
The Model 450 uses the temperature value to correct the pH
electrode slope for temperature. Be aware that pH meters do not
correct the displayed values back to what they would be at 25°C.
The ATC probe allows the meter to give the correct buffer value
for the temperature at which it is being used. When a hot or cold
sample is measured, the ATC probe will allow the meter to
correct the calibration slope to the new temperature so that the
readings are accurate for that temperature.

2
Temperature should always be recorded along with the pH value.
For others to duplicate your readings they must know what the
sample temperature was when you read it. The pH of most
samples will change with temperature and very few will change
by exactly the same amount. To know what the pH of a hot or
cold sample is at room temperature, it must be measured at
room temperature.

Buffer Temperature Correction Table

If you use standard buffers (listed below) the 450 automatically


corrects for temperature using the values shown in the table.

1.679 4.000 4.008 4.010 6.860 6.865 7.000 7.413 9.180 9.210 10.010
0°C 1.666 4.000 4.003 4.010 6.980 6.948 7.120 7.534 9.464 9.520 10.320
5°C 1.668 4.000 3.999 4.010 6.950 6.951 7.090 7.500 9.395 9.450 10.250
10°C 1.670 4.000 3.998 4.000 6.920 6.923 7.060 7.472 9.332 9.380 10.180
15°C 1.672 4.000 3.999 4.000 6.900 6.900 7.040 7.448 9.276 9.320 10.120
20°C 1.675 4.000 4.002 4.000 6.880 6.881 7.020 7.429 9.225 9.260 10.060
25 °C 1.679 4.000 4.008 4.010 6.860 6.865 7.000 7.413 9.180 9.210 10.010
30°C 1.683 4.010 4.015 4.010 6.850 6.853 6.990 7.400 9.139 9.160 9.970
35°C 1.688 4.020 4.024 4.020 6.840 6.844 6.980 7.389 9.102 9.110 9.930
40°C 1.694 4.030 4.035 4.030 6.810 6.838 6.980 7.380 9.068 9.060 9.890
45°C 1.700 4.040 4.047 4.040 6.830 6.834 6.970 7.373 9.038 9.030 9.860
50°C 1.707 4.060 4.060 4.060 6.830 6.833 6.970 7.367 9.011 8.990 9.830

109120-1 Rev. A, 11/96 15


2.6 Karl Fischer Titrations

The KF socket on the back of the meter provides a constant 1 mA


polarizing current. This output may be used to polarize metallic
electrode pairs for Karl Fischer moisture determinations or other
dead-stop titrations.

2.7 Chart Recorder


—ve

+ve

REC Socket Polarity

2
The REC socket (2.5 mm phone jack) provides a voltage
proportional to the displayed reading in pH, mV, relative mV and
concentration modes. The polarity of the output is the same as
the polarity of the input signal.

NOTE The recorder output is only available for Channel A.

Approximate Recorder Outputs


pH - Output follows display and provides approximately 60 mV
output per pH unit. This value will vary with changes in
electrode slope.

mV/relative mV - Output follows display, i.e. as display varies


from –1999.9 to 1999.9 mV, output varies from –1999.9 to
+1999.9 mV.

concentration - Output depends on valency and charge of ionic


species being measured, and is typically approximately ±60 or
±30 mV per concentration unit.

The recorder output is not available for temperature readings.

16 109120-1 Rev. A, 11/96


2.8 Interfacing via the RS232 Output

The Model 450 can transmit data in RS232C Serial format to


compatible devices such as Serial Printers and computers. The
data can be received and manipulated by most data acquisition
software packages.
The high/low limits for pH process control are available at pins 8
and 9 on the DATA socket and can drive TTL or CMOS devices.
The maximum source or sink current available is 20 mA.
The cable required for connection to IBM compatible computers
is part number 477788 and can be ordered from your distributor.
The pin configuration of that connector and Model 450 output
protocols are as follows:
Pin Signal
1 not used
2 RS232 Tx (signal transmit)

2
3 RS232 Rx (signal receive)
4 not used
5 protective ground (0V)
6 CTS (clear to send)
7 not used
8 output 1 (0V within limit, 5V below low limit)
9 output 2 (0V within limit, 5V above high limit)

Type of communication - bi directional


Baud rate - 1200 (adjustable, see Section 3.3.3)
Data format - 1 start bit
8 data bits
2 stop bits
no parity
protective ground (0V)
signal receive
signal transmit
5 1

9 6
CTS
low limit output
high limit output

109120-1 Rev. A, 11/96 17


2.8 Interfacing via the RS232 Output (cont)

Example Printout (RS232, 24 character printer)

------------------------
GLP ON GLP function selected
23/11/93 10:35:52 Date and time
ID NUMBER 09 ID number (user enterable)
MODEL M450 pH meter model number
ELECTRODE ID.......... Electrode ID (e.g. serial number)
CHANNEL A Measurement channel identifier
TEMP COMP MTC Temperature mode (manual)
CAL 1 2 5 . 0° C 7.000pH Cal point, temperature and result

OFFSET –5.8mV Electrode offset


------------------------
NAME Authorization
........................

2
GLP OFF GLP function deselected

S/N 1 10:41 23/11/93 Sample number, time and date


A 7.554 pH 2 5 . 0° C M T C Channel, result, temperature and temp. mode
M E/P Endpoint method (manual)
B 0 . 9 8 E – 4 m m o l / L 2 5 . 0° C Channel, result, temperature and temp. mode
MTC Endpoint method (manual), and electrode type
M E/P NH3-

18 109120-1 Rev. A, 11/96


2.8 Interfacing via the RS232 Output (cont)

To move around the software menu easily you can use the
numeric keypad as quick access keys. See Section 1.4 for a menu
overview, and the relevant ‘quick keys’. The 450 can also be
controlled by a PC with terminal software.
To turn on the remote function send: TON
To return to a known position in the software menu send: S (for
standby) H (for home). This returns the 450 to pH mode, channel
A measurement only.
To turn the remote function off send: X
NOTE Allow a 1 second delay between sending characters.
RS232 Keyboard Definitions
Key RS232 Key RS232 Key RS232
Command Command Command

M
<

mode U 5 5

prog P D 6 6

2
<

auto
read
A
<<
< 7 7

on/off S > 8 8

cal C 1 1 9 9

2 2 0 0
read R

3 3 - –
enter E

4 4

109120-1 Rev. A, 11/96 19


3.1 Calibration Menu

This menu allows you to set 5


calibration
calibration points for pH or
cal points concentration; recall the time and
date of the last calibration and set
last cal the isopotential point for pH.
Default refers to the factory setting
iso
which the 450 uses if no
information is entered.

3.1.1 Calibration point setting

Press enter or
< when the cal points sub routine is
highlighted.

If you enter the cal points sub routine from pH mode, the cal
points for pH calibration are set up. If you enter from
concentration mode, the concentration calibration points are set
up, and the standard set as the first calibration point is the
isopotential point.

Use and to select the calibration point you want to


<
<

change and press enter

The display flashes showing that the value can be changed. Enter
the required value using the keypad and press enter

# appears if you set a pH calibration value to a standard buffer.


The 450 stores temperature corrected values for the standard

3
buffers (see Section 2.5).

The next cal point is highlighted. If you want to change this next
point, press enter and continue as before.

Use and to select another calibration point to


<

<

change,

OR

20 109120-1 Rev. A, 11/96


3.1 Calibration Menu (cont)

3.1.1 Calibration point setting (cont)

press
< or prog to leave the sub routine without any further
changes.

Press read to return directly to measurement.

3.1.2 Last calibration recall

Press enter or
< when last cal sub routine is highlighted.

The time and date of the last calibration (pH OR concentration)


is shown. (The time and date must be set, see Section 3.3.1.)

press
< or prog to leave the sub routine.

Press read to return directly to measurement.

3.1.3 Isopotential point setting (pH)

The default isopotential point is pH7.00 (0.00mV). See Section 4


for further information.

Press enter or
< when iso sub routine is highlighted.

Press enter the display flashes showing that the value can be
changed.

3
Enter the required value using the keypad and press enter

Press read to return directly to measurement.

109120-1 Rev. A, 11/96 21


3.2 Display Menu

This menu allows you to select


display
measurement channel A, B or A &
channel B; select the units of measurement
for concentration and change the
conc units display resolution for pH mode.
Default refers to the factory
pH resolution setting, which the 450 uses if no
information is entered.

3.2.1 Channels to display

The default selection is channel A only.

Press enter or
< when the channel sub routine is
highlighted.
<

Use and to select the measurement channel(s) you


<

want to use and press enter

Press read to return directly to measurement.

3.2.2 Units for concentration to display


The default setting is no units (blank) selected. The units
available are ppm, mmol/L, % and M. eq.

Press enter or
< when the conc units sub routine is
highlighted.

3
Use and to select the units of measurement you want
<
<

to use and press enter

Press read to return directly to measurement.

NOTE Calibrate the 450 in the units you want to use for
sample measurement. Changing the units does not
change the reading; for example, the 450 will not convert
from ppm to mmol/L.

22 109120-1 Rev. A, 11/96


3.2 Display Menu (cont)

3.2.3 Resolution for pH to display


The default setting is maximum resolution.

Press enter or
< when the pH resolution sub routine is
highlighted.

Use and to select the resolution you want to use and


<
<
press enter

Press read to return directly to measurement.

3
109120-1 Rev. A, 11/96 23
3.3 System Menu

system This menu allows you to set the


time and date; set the language for
time/date the display; set the baud rate for
data output and turn the key press
language beeper on or off. Default refers to
the factory setting, which the 450
baud
uses if no information is entered.
beeper

3.3.1 Time and date

Press enter or
< when the time/date sub routine is
highlighted.

Use and to select the time display, or one of the date


<
<

options.

Press enter the display flashes showing that the value can be
changed.
Enter the time or date using the keypad and
< and press enter

For example, to enter 4/12/96:


press 0 4
< 1 2
< 9 6 enter

Press read to return directly to measurement.

3.3.2 Language

3
Default language is English.

Press enter or
< when language sub routine is highlighted.

Use and to select the language you want to use and


<
<

press There will be a short delay while


enter
the 450 initializes the language.
Press read to return directly to measurement.

24 109120-1 Rev. A, 11/96


3.3 System Menu (cont)

3.3.3 Baud rate


Default baud rate for the DATA socket is 1200. The other options
available are 300, 4800, 7200, 9600. (See Section 2.8 for further
information on the DATA socket).

Press enter or
< when the baud sub routine is highlighted.

Use and to select the baud rate you want to use and
<
<
press enter

Press read to return directly to measurement.

3.3.4 Beeper on/off

A ‘beep’ accompanies valid key presses. This routine allows you


to turn the beeper off. Default setting is beeper on.

Press enter or
< when the beeper sub routine is
highlighted.

Use and to select beeper on or off and press enter


<
<

Press read to return directly to measurement.

3
109120-1 Rev. A, 11/96 25
3.4 Temperature Menu

temptemp mode This menu allows you to select the


type of temperature probe you
ATC type want to use (standard ATC or
PT1000), or to enter the
manual temperature of solutions manually.
Default refers to the factory
setting, which the 450 uses if no
information is entered.

3.4.1 Temperature probe selection

Default probe is ATC.

Press enter or
< when the ATC type sub routine is
highlighted.

Use and to select which mode you want to use and


<
<

press␣ enter

Press read to return directly to measurement.

3.4.2 Manual temperature set


Default temperature is 25°C.

Press enter or
< when the manual sub routine is
highlighted.

Press enter the display flashes showing that the temperature

3
can be changed.
Enter the required temperature using the keypad and press enter

Press read to return directly to measurement.

NOTE Temperature can be entered manually when a


temperature probe is connected, but the 450 will use the
temperature probe value.

26 109120-1 Rev. A, 11/96


3.5 Limits Menu

This menu allows you to set high


limits
and low limits to monitor sample
alarm measurement in pH mode, and
also for temperature readings. The
set limits alarm (to alert you to ‘out of limits’
readings) can be set to show on
temp
display only, to ‘beep’ and show on
display, or it can be turned off. The
limits for pH are available at the
DATA socket. Default refers to the
factory setting, which the 450 uses
if no information is entered.

3.5.1 Alarm visual and audible on/off

Default setting is alarm off.

Press enter or
< when the alarm sub routine is highlighted.

Use and to select the alarm setting you want to use


<
<

and press enter

Press read to return directly to measurement.

3.5.2 Set high/low limits for pH

Press enter or
< when the set limits sub routine is

3
highlighted.

Use and to select high or low limit and press enter


<
<

The display flashes showing that the limit can be changed.

Enter the required limit using the keypad and press enter

The maximum limits that can be set are: high 19.999 and low
–1.999.

109120-1 Rev. A, 11/96 27


3.5 Limits Menu (cont)

3.5.2 Set high/low limits for pH (cont)


Repeat for other limit.

Press read to return directly to measurement.

The high/low limits for pH are available at the DATA socket. See
Section 2.8 for further information.

3.5.3 Set high/low limits for temperature

Press enter or
< when the temp sub routine is highlighted.
<

Use and to select high or low limit and press enter


<

The display flashes showing that the limit can be changed.

Enter the required limit using the keypad and press enter

The maximum limits that can be set are: high 130.0 and low
–30.0.
Repeat for other limit.

Press read to return directly to measurement.

3
28 109120-1 Rev. A, 11/96
3.6 Datalog Menu

This menu allows you to set up


datalog
timed measurements and print, or
on/off print and log, the last 100 results.
The data can be recalled to the
timer display, or to an external printer.
The timer must be used with the
recall data datalog function. Default refers to
clear data the factory setting, which the 450
uses if no information is entered.

3.6.1 Datalogger on/off

Default setting is data logging off.

Press enter or
< when the on/off sub routine is highlighted.

Use and to select the option you want to use and


<
<

press enter

Press read to return directly to measurement.

NOTE You can use the on/off function to temporarily stop data
logging, without cancelling the timer and other options.
Reselect an ‘on’ option to restart data logging.

3.6.2 Timer setting

Press enter or
< when the timer sub routine is highlighted.

Press enter the display flashes showing that the interval can be

press 0
changed.
Enter the timer interval using the keypad and

For example, to enter 1 hour 30 minutes 30 seconds:

1
< 3 0
< 3
< and
press enter

0 enter
3
109120-1 Rev. A, 11/96 29
3.6 Datalog Menu (cont)

3.6.2 Timer setting (cont)

Press read to return directly to measurement.

read starts and stops data logging.

NOTES Use the following checklist to make sure you have set
datalogging up correctly:
check manual endpoint facility is selected, not
automatic (see Section 2.4).
check 'datalogging on' is selected (print only or store
& print - see Section 3.6.1).
check a timer interval is entered (Section 3.6.2).
check the decimal point is flashing (i.e. the 450 is
measuring) when you return to measurement mode.

If it is not press read to start the measurement


sequence.

You can change mode, or channel, or other variables


while using the timer facility. The sample number will
restart at␣ 1.
The 450 can log up to 100 results. After 100 results the
450 starts to overwrite the first results logged. So, if for
example 150 measurements have been made, the 450
will retain the data for results 51 to 150.

3.6.3 Recall logged data

3 Press enter or
< when the recall data sub routine is
highlighted.

Use and to select recall option and press enter


<
<

If you recall the data to the external printer, it will print all the
data logged (up to 100 results).

30 109120-1 Rev. A, 11/96


3.6 Datalog Menu (cont)

3.6.3 Recall logged data (cont)

If you recall the data to the display it is shown 4 results at a

time. Use and to scroll through the results, or


<
<
press enter ‘sample number’ enter to go directly to a result.

NOTE If you have changed mode, or channel, during


measurement there will be more than one sample
number 1, etc. Press enter twice to see other samples
with the same number.

Press
< to leave the sub routine.

3.6.4 Clearing logged data

Press enter or
< when the clear data sub routine is
highlighted.

To clear all the data held in memory press enter

To leave the routine without clearing data press


<

3
109120-1 Rev. A, 11/96 31
3.7 GLP (Good Laboratory Practice) Menu

This menu allows you to set up the


GLP
good laboratory practice (GLP)
on/off function. The␣ 450 can be set to
force calibration after a preset
cal alarm time interval, after a preset
number of samples, or both. The
ID no. printout shows all the calibration
information. If using both
measurement channels (A and B)
the GLP function applies to both
channels - the channels cannot be
set up individually. Default refers
to the factory setting, which the
450 uses if no information is
entered.

3.7.1 GLP on/off

Default setting is GLP off.

Press enter or
< when the GLP sub routine is highlighted.

Use and to select GLP on or off and press enter


<
<

Press read to return directly to measurement.

3.7.2 Calibration alarm setting


<
3
Press enter or when the cal alarm sub routine is
highlighted.

Use and to select time interval or number of


<
<

samples.

Press enter the display flashes showing that the value can be
changed. The time interval can be set between
1 second and 23 hours 59 minutes and 59 seconds;
the number of samples can be set between 0 and 99.

32 109120-1 Rev. A, 11/96


3.7 GLP Menu (cont)

3.7.2 Calibration alarm setting (cont)


Enter the required value using the keypad and press enter

Press read to return directly to measurement.

After the time interval has elapsed, or the number of samples


have been measured, a message will appear on the 450 display
requesting calibration. The 450 will not allow further sample
measurement until a calibration has been carried out.

3.7.3 Entering an ID number

Press enter or
< when the ID no. sub routine is highlighted.

Press enter the display flashes showing that the number can be
changed.

Enter the required ID number (e.g. operator ID or meter serial


number) using the keypad and press enter

Up to eight digits can be entered.

Press read to return directly to measurement.

The ID number is printed with the calibration information.

3
109120-1 Rev. A, 11/96 33
3.8 Diagnostics Menu

This menu allows you to request a


diagnostics
self test - the 450 will test the
self test keyboard controls, ROM, display,
RS232 and RAM. You can also
reset reset all variable information to
the default values. Default refers
to the factory setting, which the
450 uses if no information is
entered.

3.8.1 Meter self test

Press enter or
< when the self test sub routine is
highlighted.

Press enter to enter the self test.

The 450 displays the keyboard test. Press each control and check
that the highlighting on the display goes off. When all the
controls have been checked the 450 will test the ROM (read only
memory) and then test the display.

Watch the display test, and check for any missing segments.

The 450 will then send the following characters to the DATA
socket (RS232)

0123456789ABCDEFGHIJKLMN

3
check the printout on the external printer.

The 450 finally tests the RAM (random access memory). There
will be a short delay while the RAM is tested.

A tick (✔) appears after each test.

At the end of the self test routine press read to return directly
to measurement.

34 109120-1 Rev. A, 11/96


3.8 Diagnostics Menu (cont)

3.8.2 Meter reset

Press enter or
< when the reset sub routine is highlighted.

To reset variable information to default values press enter

NOTE This will also clear any data stored during data logging.

The 450 will reset all values to default except baud rate, and
reinitialize the display.

Press
< to leave the sub routine without resetting data.

3
109120-1 Rev. A, 11/96 35
4.1 Basic Theory

pH is the unit of measurement of the acidity or alkalinity of a


solution, and is expressed as the negative logarithm of the

4
hydrogen ion concentration:
pH = –log[H+]
pH 0 is very acidic, pH 14 is very alkaline and pH 7 is neutral.

For routine pH measurements a sensing electrode and a


reference electrode or a combination electrode (both electrodes in
one body) are used along with a meter capable of displaying the
measurements.

The pH sensing electrode has an internal solution with a constant


pH value, and develops a potential when placed in a solution. This
is caused by the activity of the H+ ions in the solution. The reference
electrode has a defined, stable potential irrespective of the H+
activity in the sample. The Model 450 measures and converts the
resulting minute electrode voltages into a pH reading.

The response of a pH electrode (or its slope) is defined by the


Nernst equation:
Electrode response = E0 – 2.3RT . pH
nF
where: E0 = a constant factor T = the temperature (Kelvin)
R = the gas constant n = the ionic charge
F = the Faraday constant
The theoretical slope for an electrode is 59.16 mV where the H+
ionic charge (n) = 1 at 25°C (298K). This means that for a one
unit change in pH the system will sense a change of 59.16 mV.
The measurement of electrode slope is a good indication of
electrode condition.

Temperature is also an important consideration when measuring


pH. It affects the electrode slope. ATC probes are recommended
so that the slope can be corrected for temperature. There are
many other factors that affect pH.

Further information on pH theory and the factors that affect the


ability to do accurate pH readings is included in ‘Guide to pH
Measurement’.

36 109120-1 Rev. A, 11/96


4.2 Operating Hints

This section gives some brief operating hints and good laboratory
practices to help assure trouble free pH measurements.

1.

2.
New electrodes (or electrodes that have been in storage)
should be conditioned in one inch (25 mm) of pH 7.0 or 4.0
buffer for several hours prior to their use. Make sure that the
wetting cap has been removed from the tip of the electrode.
Always remove the wetting cap and fill hole plug during
calibration and measurements. Replace the fill hole plug
when done.
4
3. Calibrate the electrode daily. Though a one point
calibration may be suitable for some applications, we
recommend that a two point calibration (that brackets the
expected pH range) be performed.
4. Be aware that if you are measuring hot or cold samples
without the use of an ATC probe, the values displayed are
not accurate. You should be calibrating and measuring at
room temperature.
5. When transferring from one sample to another, always
rinse the electrode with distilled water and blot dry. Handle
the electrode carefully and do not use it as a stirring rod.
6. Do not use calibration buffers after the expiration date
printed on the package. Keep the bottles tightly capped and
stored according to the manufacturer's instructions. Never
put used buffer back into the bottle of new buffer.
7. For small sample volumes, make sure that both the pH bulb
and the reference junction are in contact with the sample.
8. Response time is a function of both the electrode and the
solution. Some solutions have very fast response while
others, particularly those with low ionic strength, may take
several minutes.
9. Samples must be in solution (water). You cannot measure
the pH of a dry sample.
Refer to the electrode manufacturer's instructions for proper
electrode care and maintenance. See Section 4.3.2 for general
electrode maintenance and Section 4.4.3 for problem solving.

109120-1 Rev. A, 11/96 37


4.3 Maintenance

4.3.1 Meter Maintenance

4
The Model 450 Meter needs no maintenance except for an
occasional wipe with a damp cloth. The front panel is made of
polyester and is not affected by most solvents. Polyester is known
to be affected by some organic solvents, including toluene, xylene
and methyl-ethyl-ketone. It is good laboratory practice to wipe
away any spills as soon as they occur.

4.3.2 Electrode Maintenance


CAUTION Solutions used to clean electrodes must be handled
with the care accorded to toxic or corrosive
substances.
• Do not allow the reference chamber of the electrode to dry
out. Always keep it filled with the proper fill solution.
• Formation of KCl salt at the tip and side of the electrode is
normal and should be rinsed off with warm water.
• Leave the tip of the electrode in an inch (25 mm) of pH 7.0
or 4.0 buffer when it is not being used. Do not leave it in
distilled water. For long term storage follow the electrode
manufacturer's instructions.
• If the electrode slope is off or the electrode response has
become sluggish or inaccurate, change the fill solution. If
that does not improve the response then the pH sensing
glass and the junction have probably become coated with
some of the samples being tested.
• Test the junction for flow - rinse the tip of the electrode,
blot dry and let the electrode hang in the air for 15
minutes. A proper flowing junction should have KCl salt
crystals forming on it. If none appear, review the following
suggestions for cleaning.
Protein contamination - soak the tip of the electrode for
1-2 hours in a solution of 10% Pepsin and water with
enough Hydrochloric acid added to bring the pH of the
solution to 1.0. Rinse the electrode and soak in pH 7.0
buffer until stable.

38 109120-1 Rev. A, 11/96


4.3 Maintenance (cont)
4.3.2 Electrode Maintenance (cont)
Oil contamination - Carefully clean the tip of the

4
electrode using a cotton swab soaked with alcohol or
acetone. The tip of Glass body electrodes can be put
directly into organic cleaners but do not put plastic or
epoxy body electrodes into organic solvents. Rinse the
electrode and soak in pH 7.0 buffer until stable.
All others - Soak tip of the electrode in 0.1 M
Hydrochloric acid for one hour. Rinse the electrode and
soak in pH 7.0 buffer until stable.

4.4 Problem Solving


Most problems are caused by electrode faults rather than by the
Model 450 but power fluctuations can corrupt calibration values
being held in the meter memory.

4.4.1 Meter Test


To assure that the meter memory and calibration points have not
been corrupted by power fluctuations, perform the Meter Test as
follows:

1. Press enter or
< when the self test sub routine is
highlighted, see Section 3.8.1.
The 450 tests the ROM and RAM, and allows the keyboard
controls, RS232 output and display to be checked.
2. Disconnect the electrode from the pH socket, and connect
the shorting clip (or shorting plug). Select mV mode. The
450 displays 0 ±4 mV. Disconnect the shorting clip (or
shorting plug), and the reading changes. Test both
channels.
3. Disconnect the temperature probe – the display shows
MTC. Reconnect the temperature probe (or electrode
incorporating ATC); the display shows ATC or PT1000 and
the ambient temperature.
4. Reconnect electrode.

109120-1 Rev. A, 11/96 39


4.4 Problem Solving (cont)

4.4.1 Meter Test (cont)


If the meter passes the above test the problem is electrode

4
related. Refer to Section 4.4.3 for electrode troubleshooting.
If the meter fails the above test call the number on the back of
this manual for warranty and service information.

4.4.2 Meter Error Codes


Error codes are designed to give the user information on
electrode performance problems.
E1 pH Electrode is not reading a value close enough
to the first calibration buffer. Electrode needs
maintenance (see Section 4.4.3).
E2 pH Electrode is not giving a value within 0.5 pH of
the second calibration buffer. Electrode needs
maintenance.
Ion Selective Electrode is not giving sufficient
change between calibration points. Change must
be at least 15 mV but not more than 90 mV. Check
calibration standards and electrode.
E3 Temperature of pH buffer outside limits of 0° to
50°C. Check manually entered temperature or
replace ATC probe.
E4 Calibration points must have different values.
Check cal point settings (see Section 3.1.1).
E5 pH buffer is outside range of 0 to 14. Check cal
point settings.
E6 Illegal date or time entered (see Section 3.3.1).
Measurement is out of range of the display. The
meter would display dashes if the electrode were not
in a solution, the pH of the solution is not between
-1.999 and 19.999 or if the fill solution in the
electrode is low or wrong. Dashes in the temperature
mode indicates that the ATC has failed.
Illegal limit Limit entered is outside range. Check value.

40 109120-1 Rev. A, 11/96


4.4 Problem Solving (cont)

4.4.2 Meter Error Codes (cont)

Slope is a value that compares the actual slope determined by

4
the calibration to the theoretical slope defined by the Nernst
equation. This value is displayed as a percent of theoretical and
is called electrode efficiency (see Section 4.1 for Basic Theory).
Generally the slope value can be interpreted as follows:

95 - 100% Everything is probably working fine.


90 - 95% Electrode needs maintenance. Fresh fill solution
and general cleaning.
85 - 90% Stop and do full electrode maintenance now.
Below 85% Will not calibrate. Do full electrode maintenance
or replace the electrode.

Refer to the electrode manufacturer’s instructions for full details


on maintenance, cleaning and reconditioning electrodes.

4.4.3 Electrode Problem Solving

Slow response or unstable readings in calibration buffers is


usually related to the condition of the reference fill solution or its
flow through the junction.

1. The fill solution acts as an electrical conductor between the


reference inside the electrode and the solution under test.
Empty the electrode and refill with fresh fill solution
regularly.

2. The junction is designed to allow the fill solution to leak


out of the tip of the electrode at a slow controlled rate. To
test for proper flow, rinse the tip of the electrode, blot dry
and let the electrode hang in the open air for 15 minutes. If
it is flowing properly, salt crystals of the fill solution will
form on the junction. If they do not, refer to the
manufacturer's instructions for junction cleaning or
replacement.

109120-1 Rev. A, 11/96 41


4.4 Problem Solving (cont)

4.4.3 Electrode Problem Solving (cont)

Slow response or unstable readings in samples can be caused by

4
a number of things. Those listed below assume that everything
was fine in the calibration buffers.

1. Low ionic strength samples will tend to be very drifty. You


are trying to take an electrical measurement in a solution
that is a very poor conductor. Try adding a drop of KCl fill
solution to about 5 mL of the sample. In most cases it will
not change the pH but will give the sample enough ionic
strength for the electrode to finish the reading.

2. Non aqueous samples (organics) do not follow the normal


pH scale and can cause some measuring problems. These
solutions are usually low in ionic strength, may dehydrate
the pH membrane and often cause the junction to plug due
to incompatibility with the electrode fill solution. The most
reliable way to pH organics is to dilute them with water
until stable readings can be generated.

3. Concentrated samples can cause pH measuring errors.


This is caused by problems with the pH sensing glass and
its ability to distinguish the Hydrogen ion activity over the
mass of other ions in the sample. The creation of new
junction potentials due to KCl dissociation problems can
also cause instability. The best solution is to dilute the
samples into measurable ranges.

For more information refer to the Corning Guide to pH


Measurement.

Information on ISE electrodes can be found in the Corning Guide


to ISE Measurement.

42 109120-1 Rev. A, 11/96


4.5 Meter Specifications
Operating Ranges pH Calibration
pH –1.999 to 19.999 5 point

4
mV ±1999.9 Temperature Compensation
Rel. mV ±1999.9 –5 to 105°C, automatic and
Temp. –30 to 130°C manual
Conc. 0.0001 to 19999
Display
Resolution Dot matrix LCD display
pH 0.001 / 0.01 / 0.1
mV 0.1 Outputs
Rel. mV 0.1 RS232
Recorder (Channel A only)
Temp. 0.1°C
Karl Fischer
Relative Accuracy*
Input Conditions
pH ±0.001
Impedance greater than 1012 ohms
mV ±0.2
Rel. mV ±0.2 Operating Conditions
Temp. Operating temperature: 5 to 40°C
NTC -30 - 0°C ±1% Operating humidity: max 80% at
0 - 50°C ±0.5°C 35°C (non condensing)
50 - 130°C ±1% Installation category 2
PT1000 -30 - 0°C ±0.4°C Pollution category degree 2
0 - 100°C ±0.2°C Size / Weight
100 - 130°C ±0.4°C 10 x 8 x 4 inches (255 x 200 x
Conc. ±0.5% 95 mm) / 2.9 lbs (1.3 kg)
* ±1 least significant digit
Power Requirements
Time The 450 is supplied with an
0 to 23 hours 59 minutes appropriate power supply unit, e.g.
Timer USA/Japan 100V - 120V
50/60Hz, 9VA
User selectable
0 seconds to 11 hours 59 mins Europe 230V 50Hz, 9.7VA
59 secs Output from PSU 9V DC
Memory NOTE The 450 should only be
used with the power
100 memories
supply unit provided.
Isopotential Point 450 Power Rating 4.5VA
7.000 pH, user adjustable

109120-1 Rev. A, 11/96 43


4.5 Meter Specifications (cont)

4 Regulatory Compliance
The 450 is manufactured in a FDA (Food & Drug
Administration) and ISO 9001 approved plant for Corning, and
complies with the following regulatory standards: UL1262,
CSA151, IEC1010. The 450 also complies with the European
EMC Directives and therefore carries the CE mark.

Environmental Compliance
The casework components of the 450 are marked with the
appropriate recycling identification symbol. The packaging is
manufactured using recycled cardboard, and printed with water
based ink. The packaging is recyclable. The manual is printed on
environmentally friendly paper.

44 109120-1 Rev. A, 11/96


Consumables and Accessories

Catalog # Description Quantity


477968 Automatic Temperature Probe - Basic 1
477969 Automatic Temperature Probe - PT1000 1
477389 Disposable Meter Cover 5
478109 Electrode Arm Assembly 1
477006 Electrode Fill Solution 3M KCl (125 mL) 6 bottles
477965 Electrode Storage Container 3
478353 Electrode Conditioning Solution (30 mL) 3 bottles
477989 Guide to pH Measurement 1
477959 Guide to ISE Measurement 1
476436 pH Combination Electrode, ‘3 in 1’ Refillable 1
476466 pH Combination Electrode, ‘3 in 1’ Gel 1
476146 pH Combination Electrode, Hi-Performance 1
478540 pH 4.00 Buffer (500 mL) 2 bottles
478570 pH 7.00 Buffer (500 mL) 2 bottles
478510 pH 10.01 Buffer (500 mL) 2 bottles
473651 pH 4.00 Buffer Sachets 30 packs
473650 pH 7.00 Buffer Sachets 30 packs
473652 pH 10.01 Buffer Sachets 30 packs
473676 pH Buffer Multi-Pack Sachets 32 packs
473653 pH Electrode Rinse Sachets 30 packs
471226 Power Supply, 100/120V - 50/60Hz 1
471228 Power Supply, 230V - 50Hz 1
477788 RS232C Cable 1
470109 Shorting Test Clip 3
470493 Dot Matrix Printer with Cables 1

Warranty:
Corning warrants this product to be free from defects in materials and workmanship. The
warranty period for the meter is two (2) years from the date of purchase and the probe is
six (6) months from the date of purchase.
THIS WARRANTY IS MADE IN LIEU OF ALL OTHER WARRANTIES EXPRESSED OR
IMPLIED INCLUDING THE WARRANTIES OF MERCHANTABILITY AND FITNESS FOR
A PARTICULAR PURPOSE. CORNING SHALL NOT BE LIABLE FOR ANY LOSS OR
DAMAGES ARISING FROM THE USE OF THESE PRODUCTS NOR FOR
CONSEQUENTIAL DAMAGES OF ANY KIND.
In the event that a meter or probe fails under normal laboratory conditions within the
specified period because of a defect in material or workmanship, Corning will, at its
option, repair or replace the product. Contact Corning Customer Service for return
authorization and shipping instructions at 1-800-222-7740.
© 1992. All rights reserved.
Corning Incorporated
Science Products Division
Corning, New York 14831
USA

Telephone: 1-800-222-7740 (US and Canada)


1-607-974-0353 (Outside US)

Fax: 1-607-974-0345

430 ? Rev. A, 6/96

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