Metrohm Titrino 719 S User manual

CH-9101 Herisau/Switzerland
E-Mail [email protected]
Internet www.metrohm.com
719 S Titrino
Program version 5.719.0021
Instructions for Use
8.719.1103 03.2002 / pkl

Table of contens
719 S Titrino
Table of contents
1Introduction ..........................................................................................................1
1.1 Instrument description...........................................................................................1
1.2 Controls and parts.................................................................................................2
2Manual operation..................................................................................................6
2.1 Keypad ..................................................................................................................6
2.2 Principle of data input............................................................................................7
2.3 Text input ...............................................................................................................8
2.4 Tutorial ................................................................................................................... 9
2.4.1 Entering data, setting the dialog language....................................................9
2.4.2 Development of a method, titration of an acid.............................................11
2.4.3 Storage and loading of methods .................................................................16
2.4.4 pH calibration...............................................................................................17
2.4.5 Statistics, acid capacity of drinking water....................................................18
2.5 Configuration, key <CONFIG>...........................................................................21
2.6 Selection of the mode, key <MODE> ................................................................ 24
2.7 Parameters, key <PARAM> ...............................................................................25
2.7.1 Parameters for SET ......................................................................................25
2.7.2 Parameters for MEAS...................................................................................34
2.7.3 Parameters for CAL...................................................................................... 36
2.8 Result calculations............................................................................................... 39
2.9 Statistics calculation ............................................................................................ 41
2.10 Common variables ..............................................................................................43
2.11 Data output..........................................................................................................44
2.12 Method memory, keys <USER METH> .............................................................47
2.13 Calibration data, key <CAL.DATA> ...................................................................49
2.14 Current sample data, key <SMPL DATA> .........................................................50
2.15 Silo memory for sample data ..............................................................................51
3Operation via RS232 Interface...........................................................................55
3.1 General rules .......................................................................................................55
3.1.1 Call up of objects .........................................................................................56
3.1.2 Triggers ........................................................................................................57
3.1.3 Status messages .........................................................................................58
3.1.4 Error messages............................................................................................ 60
3.2 Remote control commands................................................................................. 63
3.2.1 Overview.......................................................................................................63
3.2.2 Description of the remote control commands .............................................76
3.3 Properties of the RS 232 Interface.......................................................................95
3.3.1 Handshake...................................................................................................95
3.3.2 Pin Assignment ............................................................................................99
3.3.3 What can you do if the data transfer does not work? ................................ 101
4Error messages, Troubleshooting...................................................................103
4.1 Error and special messages.............................................................................. 103
4.2 Diagnosis........................................................................................................... 106
4.2.1 General.......................................................................................................106
4.2.2 Procedure...................................................................................................106

Table of contents
719 S Titrino
4.2.3 Equipment required: .................................................................................. 107
4.2.4 Diagnosis steps ......................................................................................... 107
4.3 Initialise and test RAM....................................................................................... 116
4.4 Releasing a locked spindle with inserted Exchange Unit ................................. 117
5Preparations .....................................................................................................118
5.1 Setting up and connecting the instruments ...................................................... 118
5.1.1 Titrino with Stirrer or Titration Stand........................................................... 118
5.1.2 Connection of a printer .............................................................................. 119
5.1.3 Connection of a balance............................................................................ 120
5.1.4 Connection of a Sample Changer ............................................................. 121
5.1.5 Connection of a recorder........................................................................... 122
5.1.6 Connection of a computer......................................................................... 123
5.2 Connection of electrodes, preparing titration vessel ........................................ 124
6Appendix ...........................................................................................................127
6.1 Technical specifications.................................................................................... 127
6.2 Pin assignment of the "Remote" socket ............................................................ 129
6.2.1 Lines of the "Remote" socket during the titration....................................... 131
6.2.2 Possible configurations of the activate pulse in SET and CAL.................. 132
6.3 User methods.................................................................................................... 133
6.3.1 General ...................................................................................................... 133
6.3.2 "Tit.HCl" ...................................................................................................... 134
6.3.3 "Tit.NaOH" .................................................................................................. 135
6.3.4 "p+m_Val".................................................................................................. 136
6.3.5 "Br_No"....................................................................................................... 137
6.4 Validation / GLP................................................................................................. 138
6.5 Warranty and conformity ................................................................................... 139
6.5.1 Warranty..................................................................................................... 139
6.5.2 EU Declaration of conformity..................................................................... 140
6.5.3 Certificate of Conformity and System Validation ....................................... 141
6.6 Scope of delivery and ordering designations ................................................... 142
Index.........................................................................................................................145

1.1 Instrument description
719 S Titrino 1
1 Introduction
1.1 Instrument description
The 719 S Titrino is a titrator to perform fast and precise endpoint titrations.
Ready-to-start methods for the most common applications are stored in the internal
method memory. The operator is free to modify and overwrite this methods or to create
and store his own titration sequences.
Data exchange with a PC is possible with the Metrodata VESUV Software and with Metro-
data TiNet Software complete remote control, data acquisition and evaluation via PC is
enabled.

1.2 Controls and parts
719 S Titrino
2
1.2 Controls and parts
Front view of instrument:

1.2 Controls and parts
719 S Titrino 3
1Exchange Unit
2Display
3Setting of display contrast
4Controls the dosing rate during manual dosing with <DOS> and subse-
quent filling
5Control keys and indicator lamps on the Titrino
Key <DOS> Dosing key. Dispensing is performed as long as <DOS> is being
pressed. Used e.g. to prepare the Exchange Unit. The dispensing
rate can be set with potentiometer (4).
Key <STOP/FILL> - Stops procedures, e.g. titrations, conditioning.
- Filling after manual dosing with <DOS>.
Key <START> Starts procedures, e.g. titrations, conditioning.
Identical with key <START> of the separate keypad.
Indicator lamps:
"Statistics" Lamp is on when the "statistics" function (calculation of mean and
standard deviation) is on.
"Silo" Lamp is on when silo memory (for sample data) is on.

1.2 Controls and parts
719 S Titrino
4
Rear view of instrument:

1.2 Controls and parts
719 S Titrino 5
6RS232 interface
for the connection of printer, balance or a computer
7Remote lines
(input/output)
for the connection of the Remote Box, Sample Changers, robots etc.
8Connection of electrodes and temperature sensor
• 2 high-impedance measuring inputs for pH and U measurements (Ind I/ Ind II).
They can either be used separately or for differential potentiometry, see page
124.
Important: If you work with both measuring inputs in the same vessel, the same
reference electrode must be used.
• 1 measuring input for polarized electrodes (Pol).
• 1 measuring input for PT100 or Pt1000 temperature sensor.
9Connection for separate keypad
10 Analog output for the connection of a recorder
11 Connection for power cable
With power supplies where the voltage is subject to severe HF disturbances, the Ti-
trino should be operated via an additional power filter, e.g. Metrohm 615 model.
12 Mains switch
13 Earthing socket
14 Connection for stirrer
728 Magnetic Stirrer, 802 Rod Stirrer, 703 or 727 Ti Stand
Supply voltage: 9 VDC (I ≤200 mA)
15 Display of the set mains voltage
Before switching on for the first time, check that the set mains voltage matches the
voltage of your power supply. If this is not the case, disconnect mains cable and
change voltage.
16 Rating plate
with fabrication, series and instrument number

2.1. Keypad
719 S Titrino
6
2 Manual operation
2.1 Keypad
The third functions (inscriptions in the triangle) on the keys of the keypad are used for
formula entry, see page 39.
CONFIG Configuration.
PARAM Parameters.
SMPL DATA Sample data.
STATISTICS ON/OFF switching of statistics calcu-
lations of consecutive determination,
see page 41.
MEAS/HOLD ON/OFF switching of measurements
between titrations and hold during ti-
trations.
SILO ON/OFF switching of silo memory for
sample data, see page 51.
CAL.DATA Calibration data, see page 49.
C-FMLA Calculation values, see page 40.
DEF Formulas, data output, see page 39ff.
USER METH Management of internal method
memory, see page 47.
PRINT Printing of reports, see page 44.
REPORTS Result output.
MODE Mode selection, see page 24.
<,> Keys for text input.
SELECT Selection of special values (dialog
marked with ":")
CLEAR Clears values, set special values.
ENTER Stores values.
STOP Stops methods.
QUIT Quits inquiries, waiting times, printing.
START Starts methods.

2.2 Principle of data input
719 S Titrino 7
2.2 Principle of data input
• If you press a key you will find the corresponding
menu in the display.
Example key <CONFIG>:
In the first line you see where you are: You pressed
key <CONFIG> and you are now in the menu "con-
figuration".
• In our example you are in the menu "configuration"
on the title ">peripheral units". By pressing
<CONFIG> you can move to the other titles of this
menu.
• If a dialog text is marked with ">", it contains a
group of inquiries. You branch into this group by
pressing <ENTER>.
Example inquiries of "peripheral units":
The first line indicates again where you are.
If a dialog text of an inquiry is marked with ":", you
can select a value with the key <SELECT>.
• A value is stored with <ENTER> and the cursor
moves to the next inquiry.
• Repeated pressing of <ENTER> moves you
through the inquiries of the group ">peripheral
units“, after the last inquiry of this group you leave
this group and return to the level above.
The next group of the menu "configuration“ appears:
">auxiliaries“
• With key <QUIT> you leave an inquiry or a group of
inquiries, it always moves you one level up.
• In this example you leave the menu "configuration"
by pressing <QUIT> and return to the display of ti-
tration mode and the chosen method.
configuration
>peripheral units
>peripheral units
send to: IBM
configuration
>auxiliaries
SET pH ********

2.3. Text input
719 S Titrino
8
2.3 Text input
<USER METH>
<USER METH>
<ENTER>
<CLEAR>
<<>
<QUIT>
<ENTER>
Example storing a method:
• Press key <USER METH>, the group ">recall
method" appears.
• Choose ">store method" by pressing <USER
METH> and press <ENTER>.
The name of the method which is currently in the
working memory is displayed.
• Delete this name with <CLEAR>.
• Open the "text writing mode" with key <<>.
• Select the character marked by the blinking cursor
with the Keys <<> and <>>, confirm it with
<ENTER>. Select the next character...
When you confirmed the last character, i.e. your
name is complete, you quit the text writing mode
with <QUIT>.
Confirm now the name with <ENTER>.
If your text fills the whole text field, just press
<ENTER> to store the text.
• During text input you can correct typing errors with
<CLEAR>:
<CLEAR> deletes the characters one by one.
• If you wish to modify an existing name (e.g. if you
have names like Text 1, Text 2, Text 3), do not delete
the existing name before you start the text input
mode. Proceed then as follows:
1. Press <USER METH>, place the cursor to
">store method" and press <ENTER>.
2. Open the text writing mode directly: Press key
<<>.
3. <CLEAR> now deletes the characters one by
one or you can add additional characters.
user methods
>recall method
>store method
method name:
>store method
method name: ABCDEFG
>store method
method name: text

2.4 Tutorial
719 S Titrino 9
2.4 Tutorial
This short operating course teaches you to work quick and efficient with the 719 S Titrino,
by means of the most important applications.
Set up your Titrino and connect the peripheral devices needed, see chapter 5.
2.4.1 Entering data, setting the dialog language
We can thus make a start and first take a look at the fundamentals of the entry of data.
We change the dialog language.
<CONFIG>
<CONFIG>
<ENTER>
<SELECT>
<ENTER>
• Switch on the Titrino. It is now in the standby state, it
shows you the active mode and method name.
• Press the key <CONFIG>, the display shows:
This is the title of the group "peripheral units". This
group contains various inquiries about peripheral
units.
• Press again <CONFIG>. You see the title of a new
group of inquiries.
This "auxiliaries" group contains the inquiry for the
dialog language.
• Pressing the <ENTER> key takes you to the inquir-
ies of the group "auxiliaries". Note the ">" sign. All ti-
tles of inquiry groups are prefixed by this sign.
This is the first inquiry of the "auxiliaries" group: the
selection of the dialog language.
• You select the various dialog languages with the
<SELECT> key. Press <SELECT> repeatedly until
"español" appears in the display.
Note the sign ":". It appears if the values can be se-
lected with the key <SELECT>.
• Accept the new "value" with <ENTER>.
The next inquiry "fecha" (date) of the group "ajustes
varios" (auxiliaries) is shown.
You can open this inquiry by pressing <ENTER>
too and go through all the inquiries of this group this
way.
configuration
>peripheral units
configuration
>auxilliaries
>auxilliaries
dialog: english
>auxilliaries
dialog: español
SET pH ********
>ajustes varios
fecha 2002-03-13

2.4. Tutorial
719 S Titrino
10
<QUIT>
<QUIT>
Because this inquiry follows no colon ":" the value
can't be selected by <SELECT>, the date "fecha"
has to be entered with the numeric keys.
• Exit the inquiries with <QUIT>. You are one level
higher in the "configuration" menu showing the title
"ajustes varios" (auxiliaries).
• Press <QUIT> once again to exit the "configuration"
menu and return to the standby state.
All the dialog texts will now be displayed in Spanish.
If you prefer English as the displayed dialog lan-
guage, proceed as before and select "English".
SET pH ********
configuration
>ajustes varios

2.4 Tutorial
719 S Titrino 11
2.4.2 Development of a method, titration of an acid
Selection of the mode
<MODE>
<ENTER>
4 ×<SELECT>
• Press <MODE> repeatedly until "SET" appears in
the display. For a description of the SET mode see
page 30ff.
• Confirm "SET" with <ENTER>
• Now select the measured quantity: Press
<SELECT> repeatedly until "pH" appears again in
the display.
Confirm the measured quantity "pH" with
<ENTER>.
Now set the end point.
Entry of the end point and the control parameters
<PARAM>
<ENTER>
<ENTER>
<ENTER>
<ENTER>
• Press <PARAM>. The display shows:
Control parameters for EP1
• Set the end point to pH = 7.00.
• Dynamics means the control range in which the
adding of the titrant is controlled in dependence on
the measured value (OFF: largest control range, i.e.
slow titration).
Set the range to 3. I.e. 3 pH units before the set EP
controlled dosing starts.
Maximum possible titration rate inside the control
range.
mode
mode SET
SET pH ********
SET: pH
SET pH ********
parameters
>SET1
>SET1
EP at pH OFF
>SET1
EP at pH 7.00
>SET1
dynamics OFF
>SET1
dynamics 3
>SET1
max.rate 10.0 ml/min

2.4. Tutorial
719 S Titrino
12
2 ×<QUIT>
Minimum titration rate inside the control range.
• Quit the inquiry with <QUIT>.
For the titration put a Exchange Unit with c(NaOH) = 0.1 mol/L on the Titrino and rinse
the tubing and the buret Tipp with <DOS>. Fill the buret again with <STOP/FILL>.
Plug a combined pH glass electrode into measuring input 1 (Ind I).
Pipette 2 mL c(HCl) = 0.1 mol/L into your titration vessel, dilute with ca. 20 mL dist. water.
Put a magnetic stirrer in the titration vessel and place buret tip and electrode in the probe,
see page 126 for their arrangement.
Start the stirrer and press <START>
During the titration the first line of the display shows the current measured value and the
volume already dispensed. The second line shows a "control bar", which indicates the
control deviation of the current measured value from the set end point.
After the titration the end point volume and its pH value is displayed.
With this end point a result can be calculated:
Calculation of the result: formula entry
<DEF>
<ENTER>
<1>
With this equivalence point a result can be calculated.
• Press the <DEF> key.
• Press <ENTER> to move on to the formula entry.
The display now shows "RS?".
• Press "1", i.e. the first formula.
You now can enter a formula. Note here the top inscrip-
tion on the keys of the keypad and the numbers. The
following symbols can be used:
EP#EP's with 1-digit number, e.g. EP1.
RS#Previously calculated results, e.g. RS1 in the sec-
ond formula.
C## Calculation constant with 2-digit number, e.g. C01.
C00 is reserved for the sample size. For the mean-
ing of the calculation constants see page 40.
def
>formula
RS?
RS1=
>SET1
min.rate 25.0µl/min
pH 2.67 0.351 ml
#======

2.4 Tutorial
719 S Titrino 13
<ENTER>
<SELECT>
<ENTER>
2 x <QUIT>
Calculate the content of your hydrochloric acid in g/L:
RS1=EP1*C01*C02/C00
End point*conc.(titrant)*molecular weight/sample size
To correct a formula, delete it with <CLEAR>.
• Confirm the formula with <ENTER>.
• You may enter a text for the result output, see page
8.
• Enter the desired number of decimal places for the
result.
• Select the desired unit g/L with <SELECT>, or type
a text as unit, see page 8.
The Titrino prompts for the calculation of the next result.
Quit the formula entry by pressing <QUIT> twice.
In order to be able to calculate the result, enter the calculation constants used in the for-
mula.
Entry of the calculation constants
<C-FMLA>
0.1
<ENTER>
36.47
<ENTER>
• Press <C-FMLA>.
The constants which have been used in the formula
are requested: input with digit keys, confirm with
<ENTER>.
C01: Concentration of your titrant= 0.1 mol/L.
Enter 0.1.
C02: Molar mass of HCl = 36.47 g/mol
Enter 36.47.
Now only the constant C00 is missing to perform the calculation. This constant is re-
served for the sample size. It can be entered directly.
RS1=EP1*C01*C02/C00
>formula
RS1 text RS1
>formula
RS1 decimal places 2
>formula
RS1 unit %
RS?
C-fmla
>C01 0.0
C-fmla
>C02 0.0

2.4. Tutorial
719 S Titrino
14
Entry of the sample size
4 x <SMPL DATA>
<2>
<ENTER>
<SELECT>
<ENTER>
• Press <SMPL DATA> repeatedly until "sample size"
appears in the display.
• Enter 2.
• Use <SELECT> to select the unit "mL" and confirm
the new value with <ENTER>.
The result is now calculated and can be displayed in place of the end point. If your
method already includes a formula at the end of the titration, the calculated result is dis-
played directly after the titration. As we have entered the formula later, we now have to
select the result display:
Display of the result
<SELECT>
<ENTER>
• Press <SELECT> repeatedly until ">display results"
appears in the display.
• Press <ENTER> to move to the result display.
If you have a printer connected, you probably wish to have the curve and a result report
printed out automatically at the end of a titration.
To install a printer, see page 119.
smpl data
smpl size 1.0 g
smpl data
smpl unit: g
SET pH ********
>display results
SET pH ********
RS1 3.71 g/l

2.4 Tutorial
719 S Titrino 15
Print reports
3 x <DEF>
<ENTER>
3 x <SELECT>
<;>
<ENTER>
<QUIT>
• Press <DEF> repeatedly until the display shows:
• Press <ENTER> to move to the definition of reports.
• With <SELECT> you select the individual repot
blocks. Use a ";" as delimiter between the report
blocks to print more than one block. If you wish to
print out a full result report, enter "full".
• Confirm the entry with <ENTER> and quit the inquir-
ies with <QUIT>.
Now print your reports by pressing <PRINT><REPORTS><ENTER>. Your printout will
look like the following:
Identification of the report type (fr=full report)
Device type, device number and program version
Initial pH value, mode and method name
Volume and pH value of EP1
Calculated result
The development of your method is now complete. Before we store it in the method
memory, you should check it again. Prepare a fresh sample and restart the titration with
<START>.
If everything appears to be all right, you can now store the method in the method mem-
ory.
def
>report
report:
report:curve;full
'fr
719 S Titrino 18200 719.0021
date 2002-03-13 time 17:34 1
pH(init) 2.40 SET pH ********
smpl size 2 ml
EP1 2.032 ml 8.14
RS1 3.71 g/l
---------------

2.4. Tutorial
719 S Titrino
16
2.4.3 Storage and loading of methods
Now store the method you have just developed in the method memory.
Storage of a method
2 ×<USER METH>
<ENTER>
<ENTER>
• Press <USER METH> repeatedly until the title
">store method" appears in the display.
• Open the inquiry with <ENTER>.
• Enter an identifier, e.g. 1 or Acid.
For text input see page 8.
The method now runs under the name "Acid". It is ready
to titrate.
If you have a printer connected, you can print out the contents of your method memory.
Key sequence: <PRINT><USER METH><ENTER>
Stored methods can be loaded at any time.
Loading a method from the method memory
<USER METH>
<ENTER>
<SELECT>
or
direct entry
<ENTER>
• Press <USER METH>. The display shows the title
">recall method".
• Open the inquiry <ENTER>
•
Y
ou can select the desired method with <SELECT>
(it shows all methods of the method memory one af-
ter the other) or by directly enter the method name.
• Load the method with <ENTER>
The method is ready to titrate.
user methods
>store method
>store method
method name: ********
SET pH Acid
user methods
>recall method
>recall method
method name: ********
SET pH Acid