Mettler Toledo DL32, DL39 Operating Instructions Manual

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Operating Instructions

KF Coulometer

DL32 / DL39

Contents

Page

1 The KF-Coulometer DL32/DL39...................................................................................5

1.1 Where can you find what information? ..........................................................................5

1.2 Coulometric determination of water - principle of measurement ........................................ 6

2 Safety Measures........................................................................................................7

2.1 Measures for your protection ........................................................................................ 7

2.2 Measures for operational safety .................................................................................... 7

3 The Coulometer .........................................................................................................8

3.1 Putting into operation .................................................................................................. 9

3.2 The operating concept ................................................................................................. 9

3.2.1 The arrow keys .........................................................................................................10

3.2.2 The command keys...................................................................................................10

3.2.3 The <Reset> key ....................................................................................................... 11

3.2.4 The key..............................................................................................................11

3.2.5 The menu keys .........................................................................................................11

3.2.6 The auxiliary function keys .........................................................................................12

3.2.7 The enter keys .......................................................................................................... 12

3.3 Changing the language .............................................................................................13

4 Setup ......................................................................................................................14

4.1 Main methods (DL39 only)........................................................................................14

4.2 Peripherals...............................................................................................................15

4.2.1 Printer .....................................................................................................................15

4.2.2 Balance ...................................................................................................................16

4.2.3 Titration stand...........................................................................................................16

4.2.4 Generator electrode ................................................................................................... 17

4.2.5 Computer ................................................................................................................. 17

4.2.6 Oven sample changer Stromboli .................................................................................17

4.3 Settings ...................................................................................................................18

5 Methods..................................................................................................................20

5.1 The KF standard method ............................................................................................21

5.2 KF method parameters ..............................................................................................22

5.2.1 No. (of the method) ..................................................................................................22

5.2.2 Title (of the method)..................................................................................................22

5.2.3 Sample parameters ...................................................................................................22

5.2.4 Speed ......................................................................................................................22

5.2.5 Mix time ..................................................................................................................22

5.2.6 Auto start (DL39 only)...............................................................................................23

5.2.7 Control parameters....................................................................................................23

5.2.8 Termination parameters .............................................................................................23

5.2.9 Blank ......................................................................................................................24

5.2.10 Drift .........................................................................................................................24

METTLER TOLEDO DL32/DL39 1

5.2.11 Result (DL32 only) ...................................................................................................24

5.2.12 Calculation 1 (DL39 only) .........................................................................................24

5.2.13 Calculation 2 / Calculation 3 (DL39 only) ................................................................... 25

5.2.14 Standby ...................................................................................................................25

5.2.15 Report .....................................................................................................................25

5.2.16 Author of the method .................................................................................................25

5.3 Storage procedures ...................................................................................................26

5.4 User and METTLER Methods (DL39 only) .................................................................... 28

5.5 METTLER methods “914 Br index” and “915 Br Blank” (DL39 only) ...............................29

5.6 METTLER Method “912 Stromboli” (DL39 only)............................................................31

6 Analysis (Run).........................................................................................................33

6.1 Starting a method .....................................................................................................33

6.1.1 Menu sequence up to standby mode (KF methods) ...................................................... 34

6.1.2 Standby mode ..........................................................................................................35

6.2 Sample determination................................................................................................36

6.2.1 Weight transfer from a balance ...................................................................................39

6.2.2 Post consumption .....................................................................................................39

6.2.3 Calculations .............................................................................................................39

6.2.4 Sample series with statistics (DL39 only) ....................................................................40

6.3 Blank determination .................................................................................................. 41

6.4 Drift determination.....................................................................................................41

6.5 Determination of bromine index (DL39 only) ...............................................................42

6.6 Sample determination with the oven sample changer Stromboli (DL39 only) ...................43

7 Auxiliary Functions (Stirrer, Pump, Results)..............................................................45

7.1 Stirrer ......................................................................................................................45

7.2 Pump ......................................................................................................................45

7.3 Results ....................................................................................................................46

7.3.1 All results .................................................................................................................46

7.3.2 Recalculation ...........................................................................................................47

7.3.3 Report .....................................................................................................................48

7.3.4 Calculations (DL39 only) ..........................................................................................48

7.3.5 Statistics (DL39 only) ...............................................................................................49

7.3.6 Statistics series (DL39 only) ...................................................................................... 50

8 Information Menu ( key) .....................................................................................51

9 Error Messages and Malfunctions .............................................................................52

9.1 Error messages from the coulometer ........................................................................... 52

9.2 Other errors and malfunctions ....................................................................................54

9.3 Checking hardware ...................................................................................................55

9.3.1 User interface ...........................................................................................................55

9.3.2 Peripheral interfaces ..................................................................................................55

9.3.3 Inputs and outputs ....................................................................................................56

2 METTLER TOLEDO DL32/DL39

10 Installation and Maintenance ...................................................................................57

10.1 Equipping the titration stand .......................................................................................57

10.2 Installing the waste bottle...........................................................................................58

10.3 Attaching the magnetic stirrer, electrodes and devices....................................................59

10.4 Maintenance and servicing ........................................................................................60

10.5 Using TTL inputs and outputs (DL39 only)...................................................................61

11 Standard and optional equipment .............................................................................63

11.1 Standard equipment ..................................................................................................63

11.2 Optional equipment ...................................................................................................64

12 Technical Data.........................................................................................................66

Index ...................................................................................................................................71

METTLER TOLEDO DL32/DL39 3

4 METTLER TOLEDO DL32/DL39

The KF-Coulometer DL32/DL39

1 The KF-Coulometer DL32/DL39

The METTLER TOLEDO DL32/DL39 coulometers are microprocessor controlled analytical instruments which you can use to perform coulometric Karl-Fischer and bromine index determinations simply, quickly and dependably.

You can attach a balance, the METTLER TOLEDO GA42 printer and a computer to the appropriate RS-232C interfaces; an EPSON- or HP-compatible printer can be attached to the Centronics interface and the METTLER TOLEDO drying oven Stromboli to the TTL-interface of the DL39.

The coulometers have a built-in tutorial, which allows you to quickly become acquainted with the instrument’s operation and method.

The two coulometers are equal in operation. Differences in hardware and software are mentioned in the corresponding sections.

These Operating Instructions correspond to software version 1.1 or higher.

1.1 Where can you find what information?

These Operating Instructions and the Help texts integrated in the titrator provide a complete description of the method of functioning of the two titrators. Explanations of parameters contained in the Help text are supplemented here when necessary.

On the memo card you can find a short overview of menus and methods. The Application Brochure explains the theoretical fundamentals of the coulometric Karl-Fischer titration as

well as the METTLER methods that are in the DL39‘s memory. The Help texts in the coulometer provide you with more information or refer you to the Operating Instructions

or the Application Brochure. You will find a detailed description of the communication between the titrator and a computer in the Description

for the computer interface.

METTLER TOLEDO DL32/DL39 5

The KF-Coulometer DL32/DL39

1.2 Coulometric determination of water - principle of measurement

When determining the water content according to Karl Fischer, water reacts with iodine and sulphur dioxide in the presence of an alcohol and a base according to the following reaction:

H2O + I2 + SO2 + CH3OH + 3 RN ➙ [RNH]SO4CH3 + 2 [RNH]I (1).

For a volumetric titration, iodine is added as titrant. In the case of a coulometric titration, the iodine is generated electrochemically by oxidation at the generator electrode:

2 I- ➙ I2 + 2 e

(2).

As long as there is water in the anolyte, the generated iodine will react according to reaction (1). I2 and H2O react with each other on a 1:1 basis. According to Faraday’s Law, the generated amount of iodine is proportional to the electric charge (10.72 mC = 1 µg H

O). Current consumption, therefore, is a measuring

stick for the amount of water. As soon as all water has been used for the reaction, a small surplus of iodine will develop in the anodic

compartment. The iodine surplus is detected by the polarized measuring electrode, and the flow of current to produce iodine is stopped.

METTLER TOLEDO offers generator electrodes with or without diaphragms. In both cases, iodine generation and detection are equal. The various applicabilities are described in the Application Brochure.

In coulometric bromine index determinations, electrochemically generated bromine reacts with the double bonds of organic compounds:

Br2 + R1-C=C-R2 ➙ R1-CBr-CBr-R2 (3).

Bromine is, thereby, produced at the anode of the generator’s electrode:

2 Br- ➙ Br2 + 2 e

(4).

The bromine index [mg bromine / 100 g sample] indicates how much bromine is consumed in the transformation of a sample according to equation (3).

Generator electrode without diaphragm

Measuring electrode

Septum

Measuring electrode

Septum

Generator electrode

with diaphragm

Titration cell

Cathode

Diaphragm

Anode

Magnetic stirring rod

6 METTLER TOLEDO DL32/DL39

Magnetic stirring rod

Safety Measures

2 Safety Measures

The titrators have been tested for the experiments and intended purposes documented in these Operating Instructions. However, this does not absolve you from the responsibility of performing your own tests of the products supplied by us regarding their suitability for the methods and purposes you intend to use them for. You should, therefore, observe the following safety measures.

2.1 Measures for your protection

- Ensure that you plug the power cable supplied into a receptacle outlet that is grounded! In the absence of grounding, a technical fault could be lethal.

Risk of electric

shock

- Never work in an environment subject to explosion hazards! The housing of the instrument is not gas tight (explosion hazard due to spark formation, corrosion caused by the ingress of gases).

Risk of

explosion

- When using chemicals and solvents, comply with the instructions of the producer and the general lab safety rules!

All Karl Fischer reagents are readily flammable and toxic.

- In the case of skin contact, immediately wash off with copious amounts of water!

- If eye contact occurs, rinse intensively with copious amounts of water and consult a physician!

2.2 Measures for operational safety

- Have the instrument serviced by METTLER TOLEDO Service only!

- Always wipe off splashed liquids immediately! The instrument is not waterproof.

- Exclude the following environmental influences:

Caution

• powerful vibrations,

• direct sunlight,

• atmospheric humidity greater than 80%,

• temperatures below 5 °C and above 40 °C,

• powerful electric or magnetic fields!

METTLER TOLEDO DL32/DL39 7

The Coulometer

3 The Coulometer

Measuring electrode

Generator electrode

Titration cell

Pump button

Keypad

Display

Rear view of instrument with connection diagram

Measuring electrode (Sensor)

External titration stand (DV705)

Cooling fin

External power pack

Waste bottle

Magnetic stirrer

GA42 printer (RS-232C) Balance (RS-232C)

Computer (RS-232C) Stromboli (TTL I/O)

Generator electrode

Stirrer

Waste bottle

(Suction fitting)

Pump unit

8 METTLER TOLEDO DL32/DL39

Socket for

external power pack

EPSON- or HP-compatible printer (Centronics)

On/Off switch

The Coulometer

3.1 Putting into operation

- Connect the supplied external power pack; switch on the coulometer. A self-test is performed before the name of the coulometer appears on the display (example DL39).

Hallo!

Arrow keys

( 8

[

Shift

) 9

] 6

CE Del

Entry keys

<Reset> key

key

Auxiliary function keys

Reset

Stirrer

Pump

Display

Results

Esc

METTLER TOLEDO

DL39

Setup

Method

Version

Run

Command keys

Menu keys

After the coulometer has been switched on, the command key <F3>, “Hello!”, the key and all menu and auxiliary function keys can be activated.

3.2 The operating concept

- Press, e.g., the setup key:

Name of the key, i.e., the displayed list of resources belongs to the setup menu

Title line

Selection bar

Resources SETUP

Main methods Peripherals Settings Help Print OK

DL32:

“Main methods” not available!

▼

Commands

Now you can also activate the <Reset> key as well as the arrow and command keys.

OK (Press <F3>): The list of selected resources appears. Print

(Press <F2>): The list of selected resources is printed (if a printer has been selected and defined).

Help (Press <F1>): Information about the selected resource appears.

METTLER TOLEDO DL32/DL39 9

The Coulometer

3.2.1 The arrow keys

▲▼

The arrow appears in the display when there are more lines to the list than are visible. When you press the arrow keys (∇∆) next to the display, the lines are scrolled downwards or upwards. The selection bar is fixed. By pressing <Shift>, ∇ or <Shift>, ∆ the lines are moved a page at a time. The commands that can be executed always refer to the line highlighted by the selection bar.

3.2.2 The command keys

The commands, which can be triggered with <F1> ... <F3> change according to the selected menu item. The following commands require an explanation:

Hello! When the instrument is delivered, the <F3> command in the initial mask “METTLER TOLEDO...”

is assigned to a tutorial menu. This is deleted when you have performed the first titration with the tutorial.

Note You can call up the tutorial at any time with the key.

OK This command is always a confirmation for what you

• wish to view,

• have viewed or entered,

• wish to adopt from a selection.

Modify When this command appears, a

• submenu can appear, which can or must be modified,

• a selection menu appears from which you can or must accept values or names,

• an existing parameter value or name can be directly replaced. If a value can be modified or entered only with the keypad, the “Modify” command is missing.

ABC This command always appears when you can select letters or characters, e.g., for a name. In

this case, you cannot enter numbers until you have confirmed “ABC” (press<F1>).

Help Information about the selected resource appears.

The <Esc> key

If you have made changes in the current menu or submenu, they are discarded, i.e., the

Esc

original values/names remain. <Esc> returns you to the previous display.

10 METTLER TOLEDO DL32/DL39

The Coulometer

3.2.3 The <Reset> key

The initial mask “METTLER TOLEDO...” reappears: <Reset> is used to terminate analyses or

Reset

other actions. Data that is not stored is lost.

3.2.4 The key

The value of the current electrolyte capacity, the last drift determination, the last blank value

determination for Stromboli (METTLER method 912), the “Hello!” tutorial, and a menu for testing the titrator hardware are accessible with this key.

3.2.5 The menu keys

In order to analyze a sample automatically, the required data must be stored. On the coulometer, this data is assigned to task areas (the menus), and can be accessed with the menu keys. Only the interaction between these menus makes automatic analysis possible.

All resources required for titration such as “Peripherals” and “Settings” are stored in the <SETUP>

Setup

menu and can be changed.

The sample is determined with the aid of a method. All methods necessary for the different

Method

analyses are stored in the <METHOD> menu and can be changed. All resources defined in the <SETUP> menu are available for these methods.

DL32 Only one method can be stored. DL39 Fifty user methods can be stored.

The titration is performed in the <RUN> menu. The method called up determines the analysis

Run

sequence.

Note Each menu is subdivided into task areas (submenus), which are designated to menus, lists or

masks in these Operating Instructions.

METTLER TOLEDO DL32/DL39 11

The Coulometer

3.2.6 The auxiliary function keys

To activate the stirrer, the pump or to recalculate results, the required commands are also assigned to menus. As they are independent of a sample analysis, but can support it, they are called auxiliary functions. They are accessible under the corresponding keys.

You can switch the stirrer on or off and change the stirring speed.

Stirrer

You can siphon off electrolyte from the cell into the waste bottle. By pressing the <Pump> and

Pump

<F3> keys, “Start” or “Stop” resp., the value of the electrolyte capacity is reset to its initial value.

You can view the result list of analyzed samples, perform recalculations, change the statistical

Results

evaluation of a series (DL39 only!) and print out additional reports.

3.2.7 The enter keys

Shift

CE Del

Shift

+ +

The <Shift> key activates the characters above the numbers.

CE You delete all entered numbers/characters/letters. Del You delete the number/character/letter last entered.

You move the cursor to the right or left (only if letters/characters are selected), see example:

moves the display up by 3 lines, moves the display down by 3 lines.

Shift

Cursor

User a

abcdefghijklm nopqrstuvwxyz ABCDEFGHIJKLM Help Select OK

12 METTLER TOLEDO DL32/DL39

The Coulometer

3.3 Changing the language

All texts on the coulometer are stored in German, English, French, Spanish, Italian and Russian. If you have not run the tutorial and understand one of the available languages better than the one displayed, you should select it:

Setup

Resources SETUP

Main methods Peripherals Settings Help OK

Resources SETUP Peripherals Settings

Settings SETUP

Language English User list Date 04-09-2001

Modify OK

– Press the <Setup> key.

– Press <Shift> and the arrow key (-) at the same time in order to scroll

down by two lines, so that “Settings” is selected.

▲

– Press <F3>, “OK”.

▼

–

Press <F2>, “Modify” repeatedly until, e.g., “Español” appears (example).

Settings SETUP

Lengua Español Lista usuarios Fecha 04-09-2001

Modif. OK

METTLER TOLEDO DL32/DL39 13

Pressing “OK” or <ESC> returns you to the “Resources” mask. OK Spanish text appears.

▼

Esc English text reappears.

Setup

4 Setup

In order to perform titrations and to enable data transmission to the peripherals, your coulometer needs to be setup with the necessary resources. In this menu, you define and store these resources.

When you press the <SETUP> key, the list of resources appears:

Main methods (DL39 only) Peripherals Settings

You can select the resources with the arrow keys and open the submenu with <F3>, “OK”.

4.1 Main methods (DL39 only)

When the titrator is delivered, the <F3> command is assigned to the “Hello!” tutorial, i.e., you can select its sequence immediately. In this menu you can assign methods to command keys <F1>...<F3> or delete “Hello!”.

With <F3>, “OK”, the following appears (example on delivery of the titrator):

Main methods SETUP

F1: Free

Modify OK

With <F2>, “Modify”, the following appears:

Main methods SETUP

User methods METTLER methods

You can select a method from the user methods, if available, or from the METTLER methods (e.g., “METTLER 912 Stromboli”:

Main methods SETUP

F1: Method 912 Title: Stromboli

Delete Modify OK

14 METTLER TOLEDO DL32/DL39

Setup

With <F3>, “OK”, the following appears:

Main methods SETUP

F2: Free

Modify OK

You can select a method to configure the <F2> command (Press <F2>, “Modify”). If you confirm this display with <F3>, “OK”, the following appears:

Main methods SETUP

F3: Hello!

Delete Modify OK

You can either delete “Hello!” with <F1> or overwrite it with another method (press <F2>, “Modify”).

4.2 Peripherals

With <F3>, “OK”, the names of the peripherals you can attach to the coulometer via the RS-232C interfaces or the Centronics interface appear. You must define these and possibly change the preset settings.

Printer None Balance None Titrn stand Internal Computer Not def.

4.2.1 Printer

With <F3>, “OK”, the name of the printer you connected to the coulometer appears.

HP GA42 EPSON None

If you select the METTLER TOLEDO GA42 there is no need for any further settings. If you select an EPSONor HP-compatible printer, you must enter the following settings (standard settings for the printer are printed in bold).

METTLER TOLEDO DL32/DL39 15

Setup

HP-compatible EPSON-compatible

Type PCL3+ or PCL3 LQ/Stylus or LX/SX Paper Single sheet Single sheet or Fanfold Format A4 or 81/2 * 11" A4, 81/2 * 11" or 81/2 * 12" Automatic feed Yes Yes or No

Type Select “PCL3+”, “PCL3”, “LQ/Stylus” or “LX/SX”. Paper Select “Single sheet” or “Fanfold. Format • A4 (width= 21 cm, length= 29,7 cm)

• 81/2 * 11" (width= 81/2 inches, length = 11 inches)

• 81/2 * 12" (width= 81/2 inches, length= 12 inches)

Automatic feed Select “Yes” or “No”.

Yes Each report starts on a new page;

with “Paper: Single sheet”, a footer is printed out on each page.

No The individual reports are separated by a distance of 2 lines.

4.2.2 Balance

Unidirect. Bidirect. None

Unidirectional The weight, the balance continuously transfers the current weight value.

Coulometer Balance

Data to Coulometer

Configuration: “Send Cont.”

Bidirectional On requesting the weight, the balance transfers the current weight value when ordered by

the titrator.

Coulometer Balance

Command from Coulometer

Data to Coulometer

Configuration: “Send Stable”

(“Send on Transfer”)

For METTLER TOLEDO balances AB, AG, AT and AX always select “Bidirectional”.

4.2.3 Titration stand

Internal External

You can attach the METTLER TOLEDO DV705 KF titration stand as an external titration stand. Its magnetic stirrer and pump are controlled via the DV705. For use of the coulometric measuring cell on the external titration stand, the titration arm must be exchanged (see optional equipment).

16 METTLER TOLEDO DL32/DL39

Setup

4.2.4 Generator electrode

For the generator electrode (with or without diaphragm) there is no need for any further settings. Note The maximum value of the current pulses of the generator electrode is 400 mA. If the conduc-

tivity of the electrolyte is low and this value can no longer be reached for this reason, the coulometer limits the current pulses to 200 mA.

4.2.5 Computer

Defined Not defined

If you connect a computer, you must select “Defined” and possibly change the settings.

Default settings for the computer

Baudrate 4800 Parity Even Number of data bits8 Number of stop bits1 Character set ASCII Start/End '{'/CR

Baudrate Select 1200, 2400, 4800 or 9600. Parity Select “Even”, “Odd” or “None”. Data bits Select 7 or 8 bits . Stop bits Select 1 or 2 bit(s). Character set Select “ASCII” or “DL”.

Note If you select “DL”, you must specify 8 for the number of data bits.

Start/End Select “'{'/CR” or “STX/ETX”.

Note You can find additional information on the communication between coulometer and the computer

in the “Description for the Computer Interface”.

4.2.6 Oven sample changer Stromboli

If you have an oven sample changer Stromboli connected to the DL 39, no further entries are necessary.

METTLER TOLEDO DL32/DL39 17

Setup

4.3 Settings

You can select or define the following settings for the coulometer:

Language English User list Date 26-08-2001 Time 10:20 Titrator-ID Access for Expert Beep Yes Capacity [mg] 80 Pumping time [s] 60

Language Select English, German, French, Spanish, Italian or Russian. User list Press <F2>, “Modify”, and a list of defined names and an empty line appears (“...”)

where you can enter a new name. Pres “ABC” and you can enter your name. Erase a selected name with “Delete”. You can then select your name for both the development of a method and the performance

of the analysis.

Date You can set the date and select the format.

Day 26 Month 8 Year 2001 Format 31-08-2001

Format Select “31/08/2001”, “08-31-2001”, “31-Aug-2001” or “Aug/31/2001”.

Time You can set the time and select the format.

Hour 10 Minute 20 Format 24 h

Format Select between “24 h” or “am/pm”.

Titrator ID To enter an identification for your coulometer , press <F1>, “ABC”. The ID is always

reported.

Access for You can decide whether all persons who work with the coulometer should also have

access to the “Setup” and “Method” menus, i.e., have the right to modify resources or methods.

Expert When the coulometer is delivered, you have access to all menus. To change

this, select “Routine”.

18 METTLER TOLEDO DL32/DL39

Routine You can:

• in the “Setup” menu, only print out the defined resources and view the list

• in the “Method” menu only print out the list of methods (DL39 only) and

• not perform any recalculations or change any statistical data.

• under the key, select neither the “Tutorial” nor the “Hardware test” .

Renewed access for experts is described on the last page of these Operating Instructions.

Beep You can select:

Yes Minimum No

Yes In addition to those cases described below under “Minimum”, a beep also

sounds after each keystroke.

Minimum A beep sounds on transition from pretitration to standby, on display of the

results and in the case of error messages.

Setup

of settings

each method.

Capacity You can perform several titrations consecutively in the same anolyte. Its capacity, however,

is limited. In the vicinity of the capacity limit the reaction rate decreases. You should enter the value for capacity that the producers of the reagents recommend.

When this value is surpassed the message “Capacity exhausted” appears. The amount of water (in mg) that has been titrated during the analyses and pretitrations

is added up. The difference between the value entered and the titrated water is displayed under the key. Pressing the <Pump> and <F3> keys, “Start” or “Stop” resp., reset the value to its initial setting.

Pumping time The defined time is a safety criterion: the pump will shut off after this time if you, e.g.,

leave the coulometer while the pump is running.

METTLER TOLEDO DL32/DL39 19

Methods

5 Methods

The coulometer automatically performs analyses with the help of predefined methods. On delivery of the instrument

in the DL32, the KF standard method specified by us is stored. You can modify this method and save it under a number.

Methods METHOD

KF standard method

Help Modify

Methods METHOD

No. 0 of the method

Help OK

When you have modified and saved the method, the following appears (example):

Methods METHOD

111 Methanol KF standard method

in the DL39 the KF standard method specified by us and 5 METTLER methods are stored. You can modify these methods and save them as user methods.

Methods METHOD

User methods METTLER methods KF standard method Help Print OK

Print The list of methods you have developed

is printed out.

OK The user methods with their defined

numbers and titles appear (example):

Methods METHOD

22 Toluene 33 Silicon oil 111 Methanol Delete Print Modify

Help Print Modify

A complete titration method comprises sample preparation, mixing and wait times, the actual titration, result calculation and a report. These partial steps are defined in the coulometer as parameters which determine the progress of an analysis.

You modify a method

by changing its parameters.

20 METTLER TOLEDO DL32/DL39

Methods

5.1 The KF standard method

You can use the KF standard method to develop your own method. In this you are guided from one parameter to another in the specified order. Exceptions are sample, control, termination and report parameters, which are shown as a group in a mask. In the case of the DL39, this also applies to the calculation parameters.

With the user and METTLER methods, all parameters appear as a list in a mask. Exceptions are again the above-mentioned groups.

The last parameter of a method, “Author of a method”, always appears in its own mask. The method is always shown with the following default parameters.

No. of the method Title of the method Sample parameters

ID Type Mass Minimum [g] 0.0000 Maximum [g] 5.0000 Entry Before

Speed [%] 40 Mix time [s] 10 Auto start No Control parameters

Pol. current [µA] 2 End point [mV] 100 Gen.speed Normal

Termination param.

Max. time [s] 300 Drift stop Rel. Drift [µg/min] 3

Blank [µg] 0 Drift Online Result

→→

→ DL39 only

→→

→ DL32 only

→→

Calculation 1 ppm

R1 = x [ppm]*f1 f1 = 1.0000 Unit ppm Decimal places 2 Statistics Yes Max. srel [%] 0.00

Calculation 2

R2 = No calculation f2 = 1.0000 Unit → DL39 only Decimal places 2 Statistics Yes Max. srel [%] 0.00

Calculation 3

R3 = No calculation f3 = 1.0000 Unit Decimal places 2 Statistics Yes Max. srel [%] 0.00

Standby Yes Report

Output Print.+Comp. Type GLP

Author of the method

METTLER TOLEDO DL32/DL39 21

Methods

5.2 KF method parameters

The following parameters can be changed. This will either cause some parameters to appear or disappear. The METTLER methods 911 – 915 and specific parameters for automation with the METTLER TOLEDO oven sample changer Stromboli are described in a separate chapter.

5.2.1 No. (of the method)

The method is stored under the number. The numbers 911– 915 are reserved for METTLER methods.

5.2.2 Title (of the method)

You can give the method a specific name.

5.2.3 Sample parameters ID You can enter an identification for the sample(s) now or just before the titration (“Request”)

for every sample.

Type Select “Mass”, “Fixed mass”, “Volume”, “Fixed volume”, “Pieces” or “Fixed pieces”. Minimum/Maximum

appears when “Mass”, “Volume” or “Pieces” is selected. The unit depends on the

type of sample: [g], [mL] or [pcs]..

Help You can calculate and enter values for a fixed or variable amount of sample.

Entry of the amount of sample “Before” or “During” the actual titration. “Entry” appears when

“Mass”, “Volume” or “Pieces” is selected. DL39: If you select “Yes” for the parameter “Auto start” (see below), “Before” is automatically

converted to “During” when storing.

Density appears when “Volume” or “Fixed Volume” is selected. Weight appears when “Fixed Mass” is selected. Volume appears when “Fixed volume” is selected. Number appears when “Fixed pieces” is selected.

5.2.4 Speed

Stirring should guarantee quick and thorough mixing of the electrolyte. We recommend the setting: 40 %. The magnetic stirring rod should not “jump”.

Only use the magnetic stirring rod included in the delivery (see equipment).

5.2.5 Mix time

The time is an empirical value and can be entered individually for the samples (“Request”).

22 METTLER TOLEDO DL32/DL39

Methods

5.2.6 Auto start (DL39 only)

Yes The DL39 begins analysis as soon as a sample has been added. The time for adding a sample may not exceed 30 seconds or the instrument will revert to its “Standby” mode.

5.2.7 Control parameters

Pol. current Select 1,2 or 5 µA for polarization current. End point For the end point we recommend a value of 100 mV.

The recommended values for both types of generator electrodes (with or without diaphragm) are in bold print.

Pol. current [µA] 1 2 5 End points [mV] 100 100 100

Gen. speed Select “Normal”, “Fast” or “Slow” for the titrant generation (iodine or bromine).

Normal This setting is optimized for the determination of water in the µg and lower

mg range.

Fast Select this setting for larger amounts of water in order to shorten the analysis. Slow Select this setting for smaller amounts of water.

1000 µg50 µgH2O content of the sample

Generation speed

Slow FastNormal

5.2.8 Termination parameters

To terminate the titration, you must define “Max. time [s]” and “Drift stop” (“Delay” respectively) as a condition. After reaching the end point, the titration is terminated when the first of the selected conditions is met.

Max. time As a safety measure, you must enter a value for the maximum time of analysis. If no end

point can be found, the analysis will be terminated after this time has run out.

Drift stop Select “Absolute”, “Relative” or “No”.

Relative Termination when actual drift is less than the drift measured before the

titration(D0) plus the entered value (Di): D < D0 + Di.

Absolute Termination when the drift is less than the entered value (Di): D < Di. No “Drift [µg/min]” disappears and “Delay [s]” appears.

Delay If you enter “0” for the delay time, the titration is terminated as soon as the end point is

reached. This could result in premature termination of the titration.

METTLER TOLEDO DL32/DL39 23

Methods

5.2.9 Blank

For the entry of a correct value, you should perform a determination. You can enter the value specific to the sample (“Request”).

[mg] You can enter a value in the method. Request Before each titration, the value is requested individually for each sample.

5.2.10 Drift

The drift value is needed for calculation of the result. You can enter a value (“[µg/min]”) in the method or just before every titration (“Request”) or have it entered automatically:

[µg/min] You can enter a value in the method. Request Before each titration, the value is requested individually for each sample. Online The moisture that enters the titration vessel is continuously measured, evaluated and

displayed in the standby mode.

Determination Some standard operating procedures require insertion of the value of a drift determination.

If you have performed a drift determination, the result is stored under the key and used in the calculation.

5.2.11 Result (DL32 only)

The water content is calculated with the appropriate formula by selection of the unit: [mg], [µg], [%], [ppm], [mg/pc], [mg or µg] and [% or ppm].

[mg or µg], [% or ppm] With the following limit values, the result is automatically set from one unit to

the other.

mg µg % ppm

smaller than 0,1 → 99,.. smaller than 0,1 → 999,.. 0,1.. ← larger than 100 0,1.. ← larger than 1000

5.2.12 Calculation 1 (DL39 only) R1 Result of the first calculation: The water content is calculated with the appropriate formula

by selection of the unit: [mg], [µg], [%], [ppm], [mg/pc], [mg/g], [min], [ppm]ext.extr., [ppm]ext.soln., [%]ext.extr., [%]ext.soln.

[min] Duration of the titration. [ppm]ext.extr., [ppm]ext.soln., [%]ext.extr., [%]ext.soln. Special calculation for

samples that are used after an external extraction or external dissolution. The second and third calculations are needed. See Application Brochure.

Unit You can enter a user-defined unit (e.g., “g” if you define a factor of 0.001 for the calculation

of the H2O content in [mg]) .

24 METTLER TOLEDO DL32/DL39

Methods

Statistics

To obtain the mean value x, the standard deviation s and the relative standard deviation srel, of a sample series, you must select “Yes”. You can terminate a sample series using the auxiliary function “Results”.

Max. srel If the entered value for the max. relative standard deviation is exceeded, a message appears.

5.2.13 Calculation 2 / Calculation 3 (DL39 only)

The available parameters are the same as for calculation 1. Instead of a formula, you can select “No calculation”. The water content is calculated with the appropriate formula by selection of the unit: [mg], [µg], [%], [ppm], [mg/pc], [mg/g], [min]. The following units are missing: [ppm]ext.extr., [ppm]ext.soln., [%]ext.extr., [%]ext.soln.

Note You cannot determine samples from an external extraction or dissolution in the routine mode as

you must enter the amount of sample for the extraction/dissolution and the amount of solvent under calculation 2 and 3.

5.2.14 Standby

Yes After a titration, the cell is kept anhydrous. We recommend allowing the standby titration to run

even during lengthy pauses so that you can start the next titration at any time.

No After a titration the start mask of the analysis menu reappears. [min] After the sample determination, a switch is made to the standby mode and the subsequent rate

of consumption is displayed and printed out every minute for the defined time.

5.2.15 Report

Output Select “Printer”, “Computer” or “Print.+Comp.” as output device. Type DL32 Select “GLP”, “None” or “Short-form.

DL39 Select “GLP”, “GLP+curves”, “None” or “Short-form”. Curves can only be printed

out on an EPSON or HP compatible printer.

(GLP report: All data which is required by the rules of Good Laboratory Practice.)

5.2.16 Author of the method

By selecting your name from the user list, you can document that you are responsible for the development of the method.

METTLER TOLEDO DL32/DL39 25

Methods

5.3 Storage procedures

The following always appears as the last parameter of a method:

Methods METHOD

Author of the method

Help Modify OK

The modified method is stored when you confirm by pressing <F3>, “OK”. Examples:

DL32 DL39

Methods METHOD

111 Methanol KF standard method

Help Print Modify

Methods METHOD

22 Toluene 33 Silicon oil 111 Methanol Delete Print Modify

If you have not entered any or a wrong method no., the following appears:

Error

No/invalid value Min.: 1.00000 Max.: 899.000

– Confirm the error message by pressing <F3>, “OK”.

Method METHOD

No. 0 of the method

– Enter the number and confirm by pressing <F3>, “OK”. The method is stored.

26 METTLER TOLEDO DL32/DL39

Methods

If you have entered a method no. that already exists (DL39 only), the following appears:

Method 22 METHOD Method exists! Change number Overwrite method

Change number The mask “No. of the method” reappears. You can now enter a new number. Overwrite method The new or modified number is stored. The old method with the same number

is overwritten.

While you are modifying a user or a METTLER method, you can press the <Run> key in order to start an analysis (the <Setup> and <Auxiliary functions> keys are blocked).

• If you have not yet modified any parameter of the method, the start mask of the “Analysis” menu appears.

• If you have already modified a parameter of the method, the mask “Author of the method” appears. The

method is stored with <F3>, “OK”, and the start mask of the “Analysis” menu is displayed.

METTLER TOLEDO DL32/DL39 27

Methods

5.4 User and METTLER Methods (DL39 only)

The following methods have been developed by us and can be performed immediately (see Application Brochure):

911 Standard 1.0 912 Stromboli 913 Ext.Extr. 914 Br Index 915 Br Blank

You can modify METTLER methods, but in this case you must always give them a new number (1– 899) so that they are stored as user methods.

You can print out the selected methods by pressing <F2>, “Print”.

User methods can be deleted (only in expert mode).

Methods METHOD

22 Toluene 33 Silicon oil 111 Methanol Delete Print Modify

If you press <F1>, “Delete”, the following appears:

Delete? METHOD

Yes No

Yes Pressing <F3>, “OK”, will delete the method. No Pressing <F3>, “OK”, will bring up the list of methods.

The method is not deleted.

METTLER methods cannot be deleted.

Methods METHOD

911 Standard 1.0 912 Stromboli 913 Ext.Extr.

Print Modify

28 METTLER TOLEDO DL32/DL39

Methods

5.5 METTLER methods “914 Br index” and “915 Br Blank” (DL39 only)

If you wish to develop a bromine index determination to meet your requirements, you can modify METTLER method 914 and 915 and store them as user methods.

No. 914 Title Br Index Sample parameters

ID Request Type Mass Minimum [g] 0.2000 Maximum [g] 0.4000 Entry Before

Speed [%] 40 Mix time [s] 120 Control parameters

Pol. current [µA] 2 End point [mV] 100 Gen.speed Normal

Termination param.

Max. time [s] 6000 Delay [s] 15

Blank Request

Calculation 1

R1 = x[Br index]*f1 f1 = 1.0000 Unit Decimal places 2 Statistics Yes Max. srel [%] 0.00

Calculation 2

R2 = No calculation f2 = 1.0000 Unit Decimal places 2 Statistics No Max. srel [%] 0.00

Calculation 3

R3 = No calculation f3 = 1.0000 Unit Decimal places 2 Statistics No Max. srel [%] 0.00

Report

Output Print.+Comp. Type GLP

Author of the method

No. 915 Title Br Blank Sample parameters

ID Request Type Fixed Volume Density [g/mL] 1.000 Volume [mL] 100

Speed [%] 40 Mix time [s] 120 Control parameters

Pol. current [µA] 1 End point [mV] 100 Gen.speed Normal

Termination param.

Max. time [s] 6000 Delay [s] 15

Calculation 1

R1 = x[mg]*f1 f1 = 1.0000 Unit mg Decimal places 2 Statistics Yes Max. srel [%] 0.00

Calculation 2 Calculation 3 Report

Output Print.+Comp. Type GLP

Author of the method

Pretitration This parameter is not applicable. Autostart This parameter is not applicable. Pol. current Measurement results and endurance of the measuring electrode are ideal at a polarization

current of 1µA.

Gen. rate The speed of bromine generation at the anode of the generator electrode. For bromine

determinations the setting is fixed at “Normal”.

Delay Desired time of delay [s] after reaching the end point. Drift and driftstop are not applicable. Blank The value determined as a blank (METTLER method “915 Br Blank”) can be determined

before the start of an analysis in the method, or it can be entered before the titration (“Request”).

Drift This parameter does not apply because bromine determinations do not have a drift.

METTLER TOLEDO DL32/DL39 29

Methods

R1 Result of the first calculation: the bromine index [Br-Index] is calculated according to the

selected formula.

Unit The bromine index and the bromine number are quantities without dimension.

The bromine index is the amount of bromine in [mg] reacting with 100 g of sample. The bromine number is the amount of bromine in [g] reacting with 100 g of sample.

Standby This parameter does not apply. Author “Author of the Method” only appears if you change the method.

Specific parameters for the blank determination with “915 Br Blank”. Type Select “Fixed volume” because the measuring cell is filled with 100 mL of solvent. Volume Select “100” because the measuring cell is filled with 100 mL of solvent. Blank This parameter does not apply. R1 The blank value is measured in [mg] and is needed for the calculation of the bromine

index.

30 METTLER TOLEDO DL32/DL39

Methods

5.6 METTLER Method “912 Stromboli” (DL39 only)

If you wish to develop an automatic determination of the water content of thermally stable liquids or solids, you can modify the METTLER method “912 Stromboli” and store it as a user method.

No. 912 Title Stromboli Sample parameters

Type Mass Minimum [g] 3.0000 Maximum [g] 8.0000

Speed [%] 40 Mix time [s] 300 Set temperature 250 Control parameters

Pol. current [µA] 2 End point [mV] 100 Gen.speed Normal

Termination param.

Max. time [s] 600 Driftstop Rel. Drift [µg/min] 10

Blank Request Drift Request

Calculation 1 ppm

R1 = x[ppm]*f1 f1 = 1.0000 Unit ppm Decimal places 3 Statistics Yes Max. srel [%] 0.000

Calculation 2

R2 = No calculation f2 = 1.0000 Unit Decimal places 2 Statistics Yes Max. srel [%] 0.00

Calculation 3

R3 = No calculation f3 = 1.0000 Unit Decimal places 2 Statistics Yes Max. srel [%] 0.00

Report

Output Print.+Comp. Type GLP

Author of the method

Sample parameters The sample parameter “ID” and “Entry” are not applicable. Mix time The time (in seconds) during which the water in the sample evaporates completely

and dissolves into the solvent in the measuring cell.

Autostart This parameter is not applicable because the sequence of the sample series is

controlled automatically.

Set temperature

Enter the set temperature in °C at which the H

O determination is to be performed.

The set temperature can be selected anywhere between 50 and 300 °C. This value cannot be changed within a series. The set temperature is noted in the titration report.

Blank The blank value [µg] is made up of the H

O content of the carrier gas (time

dependent) and the H2O content of the sample vial (time independent). The termination is like a “normal” sample determination with defined method parameters and, therefore, can be integrated into the sequence of a series. Drift is deducted from the result making the blank an absolute value independent of time. The blank value for Stromboli can be viewed at any time by pressing the key.

METTLER TOLEDO DL32/DL39 31

Methods

DeterminationThe value is automatically determined before the sample series and stored

for calculating the results.

Request The value is requested before the series. No The most recently stored value is used.

Note For a onetime blank determination for various sample series the blank value can be determined

individually. To do this, a method is built selecting “Determination” for the blank parameter. When prompted to enter the number of samples under the sample parameters, enter “0”. The resulting blank value is stored, i.e., it is available for all following sample series and can be viewed at any time by pressing the key.”

Drift

The drift can be determined manually in the standby mode at any time (press <F1>, “Drift”), or automatically before each series.

DeterminationValue is determined automatically before the sample series and stored for

the calculation of the results.

Request Value is requested before the series.

No The most recently stored value is used. Standby This parameter is not applicable because no post consumption measurement is performed. Report The results are printed at the end of a series. Author “Author of the Method” only appears if you modify the method.

At the beginning of a sample series, the following parameters are required as long as “Request” has been selected for them in the method.

Blank [µg] Drift [µg/min] ID (text) Number of samples (max. 13) Sample parameter (mass, volume, pieces, etc.)

32 METTLER TOLEDO DL32/DL39

Analysis (Run)

6 Analysis (Run)

You perform titrations with a selected method. The required data is stored in the “Method” and “Setup” menus. While an analysis is running, all menus and auxiliary functions are blocked.

6.1 Starting a method

When you press the <Run> key, the start mask appears:

DL32 DL39

Start RUN

Method No. 0 Title User Help OK

Start RUN

Method No. 0 Title User Help Modify OK

The method number

• of “O” is entered if no method (DL32) or no user method (DL39) is stored.

• of the stored method (on the DL32) is always automatically entered together with the title.

• on the DL39 is always the number you either entered directly or accepted from a METTLER or user

method.

Notes

• You can select the user name. The name that was selected in the analysis last performed remains stored.

• DL39: The start mask always shows the number of the method with which an analysis was last per-

formed, e.g., method no. 22. If you delete this, “Method not available” appears when you confirm the mask with “OK”.

METTLER TOLEDO DL32/DL39 33

Analysis (Run)

6.1.1 Menu sequence up to standby mode (KF methods)

Example:

Start RUN

Method No. 22 Title Toluene User K. Lips Help Modify OK

PRETITRATION RUN

You start the pretitration by pressing <F3>, “OK”, (DL32: “Modify” is missing).

Pretitration is always executed with the control parameters of the selected method. The electrolyte is titrated until anhydrous.

Potential [mV] 325 Help

STANDBY RUN

The actual potential is displayed. Transition to standby mode is automatic.

The arrows beside the drift value indicates the drift status:

Active Method 22 Potential [mV] 98 Drift [µg/min] 1 ➙ DRIFT SAMPLE

➘ Wait. Drift is decreasing! ➙ This arrow indicates that you can start a determination. ➚ Wait. Drift is increasing!

Start a drift determination by pressing <F1>, “DRIFT”. Start a sample determination by pressing <F3>, “SAMPLE”.

Note If the pretitration lasts longer than 30 minutes, a message appears. After confirmation with

“OK”, the pretitration starts again. In such a case, you should check whether, e.g., all connections of the titration stand and cell are tight.

34 METTLER TOLEDO DL32/DL39

Analysis (Run)

6.1.2 Standby mode

During standby, the following menus are blocked or selectable:

Blocked <Setup>, <Pump> and, via the key: “Hello!” and “Hardware test”. Selectable <Stirrer>, <Results>, <Method>, <RUN> and key (except “Hello!” and “Hardware test”.

Stirrer

You can change the speed of the stirrer. This is reported for the subsequent sample determination.

Results

The menu is not shown until you have performed the first measurement or a result is available.

Method You can modify all methods. Within the active method, you cannot modify the following parameters:

• Polarization current

• End point

The modified parameters are adopted for the next sample. For documentation conforming with GLP, you should print out the method before you switch back to the “Run” menu.

Note (DL39 only) If you change parameters of an active method, the sample series will be

terminated. If you restart a method, the results of the current series are deleted.

METTLER TOLEDO DL32/DL39 35

Analysis (Run)

6.2 Sample determination

With <F3>, “OK”, or <Run> you start a sample determination. According to the selected method, the following masks may appear.

In succession, specific parameters are requested if defined in the method as “Request”. Example:

ANALYSIS RUN

Mix time [s] 10

Then one of the following mask appears:

ANALYSIS RUN

Weight [g] 0 Minimum [g] 0.3750 Maximum [g] 0.8750 Help Bal. OK

The mask for the sample entry appears if a variable amount of sample is defined with “Entry: Before”.

ANALYSIS RUN

Please add sample

0.3750 g -

0.8750 g

Help OK

The mask for sample addition appears if a variable amount of sample is defined with “Entry: During” (example: mass)

Note

• If you take longer than five minutes for the entry of samples or sample-specific parameters, the coulom-

eter switches back to the standby mode.

• If you have selected “Autostart: Yes” in the method, the sample must be added within 30 seconds.

Otherwise, the coulometer returns to the standby mode.

• If you accidentally add a sample while the titrator is in the standby mode, the coulometer will begin a

“Pretitration”, i.e., it will titrate all the water out of the sample. You can salvage the situation (“Emergency

analysis”) by pressing the <RESET> key first and then the <SHIFT> and <RUN> keys simultaneously. One of the above displays will appear, i.e., pretitration and standby mode are skipped. Thus, your sample is not “lost”.

36 METTLER TOLEDO DL32/DL39

Sequence of sample determination Example (with “Weight: before”):

Analysis (Run)

ANALYSIS RUN

Weight [g] 0 Minimum [g] 0.3750 Maximum [g] 0.8750 Help Bal. OK

Pressing <F3>, “OK”, will bring up the following mask appear.

ANALYSIS RUN Add sample or confirm addition:

0.3750 g -

0.8750 g

Help OK

Pressing <F3>, “OK”, confirms addition of the sample and starts the analysis.

ANALYSIS RUN

Sample Drift

The values and the limits for the weight are adopted from the defined sample parameters of the method.

If you have attached a balance, you can transfer the value displayed on the balance (weight of the sample) by pressing <F2>, “Balance”.

It is possible to enter the amount of the sample during analysis. Pressing <F1>, “Sample”, the parameter “Weight [g]” or “Volume [mL] is displayed for you to enter the value.

During titration you can switch to four different displays:

ANALYSIS RUN

Drift: 95 µg/min

Sample Cont. Graph

ANALYSIS RUN

Duration: 1 min

Sample Pot. OK

Drift Current generation rate. Content H2O content titrated so far. Duration Measuring time from beginning of data logging (excluding mixing time!).

Note The time value printed in the report includes mixing time!

Potential Potential measured at the measuring electrode.

ANALYSIS RUN

Content:

42.0012 µg

Sample Dur. OK

ANALYSIS RUN

Potential: 400 mV

Sample Drift OK

METTLER TOLEDO DL32/DL39 37

Analysis (Run)

Titration is ended in accordance with the defined termination parameters. In the background, the coulometer goes back into the standby mode.

Report RUN

Printing...

The result is printed out and displayed.

Result RUN

Method 22 Sample 1 R1 = 1.98 %

If you confirm with “OK”, one of the following is displayed:

• the standby mask (method parameter “Standby: Yes”), or

• the start mask (“Standby: No”), or

• the post consumption mask (method parameter “Standby: [min]).

The result is now stored under the auxiliary function “Results” so that you can, e.g., perform recalculations.

38 METTLER TOLEDO DL32/DL39

6.2.1 Weight transfer from a balance

Analysis (Run)

ANALYSIS RUN

If you press <F2>, “Balance”, in the corresponding mask, the value displayed on the balance appears. It is accepted with “OK”.

> 1.2345 g

6.2.2 Post consumption

STANDBY RUN Post consumption: Duration: 0:34 min Drift: 6 µg/min

Stop

If you have selected “Standby: [min]” in the method, the subsequent measurement of the drift is performed directly after the sample determination, and a drift value is automatically printed out every minute.

6.2.3 Calculations DL32 (without Auto start) / DL39 (“Auto start: No”)

If you press <F3>, “Sample”, or the <Run> key in the standby mode, measurement of the time needed for calculation of the drift compensation starts. It is stopped as soon as the titration has ended.

<F3>, “Sample”,

or <Run>

Standby

<F3>, “Sample”,

Request and adding of sample

or <Run>

Mix time

Titration

Generation of titrant

“Duration” (Display)

“Duration” (Calculation/Report)

DL39 (“Auto start: Yes”)

In the case of an automatic start of the titration (“Autostart: Yes”), measurement of the time (“Duration”) needed for the calculation of the drift compensation starts with the request for the sample. It is stopped as soon as the titration has ended.

<F3>, “Sample”,

Standby

or <Run>

Requests

Waiting for addition of sample (max. 30 s)

Sample

addition

Mix time

Titration

Generation of titrant

“Duration” (Display)

“Duration” (Calculation/Report)

METTLER TOLEDO DL32/DL39 39

Analysis (Run)

H2O content in µg

O [µg] = (consumption [mC] / 10.72 [mC/µg]) – (drift [µg/min] * duration [min]) – (blank [µg])

To get the H2O content in mg, divide by 1,000.

H2O content in %

H2O [%] =

((consumption [mC] / 10.72 [mC/µg]) – (drift [µg/min] * duration [min]) – (blank[µg]))

mass [g] * 10

[µg/g]

100 [%]

To get the H2O content in ppm, multiply the formula by 10,000, for the H2O content in g/kg, multiply by 10.

H2O content per piece

O [µg/pc] =

(consumption[mC] / 10.72 [mC/µg]) – (drift [µg/min] * duration [min]) – (blank [µg])

number of pieces [pcs]

These parameters are listed on every GLP report to allow you to double-check the result.

6.2.4 Sample series with statistics (DL39 only)

If you have selected “Statistics: Yes” in the method under Calculation 1, 2 or 3, results and statistical data of the sample or concentration determinations are stored under the auxiliary function “Results”.

The series is terminated, if you

• enter the corresponding command in the auxiliary function “Results”,

• change the method parameters of the active method,

• select a different method,

• switch off the coulometer.

The series is not terminated if you stop a determination by pressing <Reset> and perform the next determination under the same method.

Note You can perform a series with a maximum of 99 samples. The last 60 results are stored.

40 METTLER TOLEDO DL32/DL39

After, e.g., the third sample determination, the following appears:

Result RUN Method 22 Sample 3 R1 = 1.91 %

Analysis (Run)

x OK

<F1> Allows you to toggle between displaying results or statistics.

Statistics RUN Method 22 R1 n = 3 x = 1.95 % s = 0.010901 % Result OK

Note The mean is calculated after two samples; after three samples, the absolute and relative stan-

dard deviation are computed.

6.3 Blank determination

If you have dissolved a sample in a solvent with a H2O-content unknown to you, run an analysis with only the solvent and without the sample. The obtained value can be entered as a blank before each titration (“Request”) or can be entered automatically (“Determination”). This blank value is included in the calculations.

The blank value of the METTLER method “912 Stromboli” is stored under the key.

6.4 Drift determination

You must determine the drift when “Drift: Determination” is defined in the method. By pressing <F1>, “DRIFT”, the following appears:

DRIFT RUN

Duration: 2:21 min Help

The bar will fill according to the time elapsed. After 3 minutes, the result is printed and displayed. Simultaneously, the value is stored under the key.

METTLER TOLEDO DL32/DL39 41

Analysis (Run)

6.5 Determination of bromine index (DL39 only)

The bromine index distinguishes itself from a KF titration by different method parameters and the missing display of “Drift”, “Content” and “Duration” during the analysis. Because the determination of the bromine index does not have a drift, it cannot be used as a termination parameter.

Note Because it is easier to clean we recommend using a generator electrode without diaphragm for

bromine index determinations.

Start RUN

Method No. 914 Title Br Index User Mi Hoa Help Modify OK

ANALYSIS RUN

If the parameters of the method have been defined with “Request”, they are displayed before the screen to enter the sample appears (example “Mass”

Weight [g] 0 Minimum [g] 0.2000 Maximum [g] 0.4000 Help Bal.* OK

and “Entry: Before”).

* only appears if a balance has been defined.

After you have confirmed the sample addition with <F3>, “OK”, the titration will begin.

ANALYSIS RUN

Analysis running...

** only appears if you have not entered the sample size. Press <F1>,

Potential [mV] 580 Sample**

Result RUN Method 914 Sample 2 Br Index = 370

“Sample”, the parameter “Weight [g]” appears for you to enter the value.

After the titration, the result is recorded before it is displayed.

Pressing <F3>, “OK”, will return you to the starting screen.

42 METTLER TOLEDO DL32/DL39

Calculation formula

Analysis (Run)

Bromine index =

100 * (0,0008281 [mg/mC] * consumption [mC] – blank[mg])

weight of sample [g]

Blank [mg] = 0,0008281 [mg/mC] * consumption [mC]

bromine index [mg Bromine / 100 g sample]

Bromine number [g Bromine / 100 g sample] =

1000

Note Bromine molar mass: 79,9 [g/mol] 79,9

= 0,0008281 [mg/mC]

Faraday constant: 96485 [C/mol] 96485

6.6 Sample determination with the oven sample changer Stromboli (DL39 only)

The oven sample changer Stromboli is used in combination with the DL39 coulometer for the automatic determination of H2O content of thermally stable liquids and solids. In order to do this, the sample is heated in the oven and the evaporated water is transported into the measuring cell by means of a dry inert gas stream. The DL39 controls all of Stromboli’s functions via the METTLER method “912 Stromboli”. Using this method as point of departure, user methods can be developed allowing automatic determination of sample series with up to 13 samples as well as drift and blank determinations. Prior to determination, Stromboli automatically inserts the sample vials on the sample rack into the oven.

The result of a sample determination with Stromboli is made up of H2O content of the sample, blank value (H2O content of an empty sample vial), and drift value (H2O content of the carrier gas).

A drift determination is automatically performed if “Drift: Determination” was selected in the method. The drift can also be determined manually at any time in the standby mode (Press <F1>, “Drift”). In both cases, the determination is performed with the sample vial in the “Drift” position. The vial is inserted into the oven and the determination is performed for three minutes after reaching the set temperature entered in the method. The result is stored (i.e., it is available for subsequent sample series) and can be viewed by pressing the key (including date and time of determination).

A blank determination is automatically performed if “Blank: Determination” was selected in the method. The determination is performed with the sample vial in the “Blank” position (empty sample vial). The determination is performed like a normal sample determination and, therefore, can be integrated into the sequence of a series. The blank value is defined as sample “0” without any content parameters and the default parameter “ID: Blank”. The result of the blank determination is stored and can be seen under the sample number “0” in the titration report or viewed by pressing the key (including date and time of determination).

METTLER TOLEDO DL32/DL39 43

Analysis (Run)

Sequence of a sample series

When starting a method from the idle state, the entered, set temperature is conveyed to the oven. The sample vial in position “Drift” is inserted into the oven and the oven heats up to the set temperature during pretitration, i.e., in the standby mode. The temperature display flashes on the Stromboli, and the display alternates between current temperature and set temperature.

After reaching a constant drift at the set temperature, the sample series can be started from the standby mode by pressing <F3>, “Sample”. The analysis will only begin when the oven has reached the set temperature. Until the set temperature has been attained (can take several minutes), the message “Waiting for Stromboli” appears.

ANALYSIS #01 RUN ID Weight [g] 0 Minimum [g] 2.000 Maximum [g] 4.000 Bal.* Start OK

No.ID Status 0 Blank Done 1 Active 2 Ready 3 Ready

Modify OK

Sample 1 RUN ID Weight [g] 0 Minimum [g] 2.000 Maximum [g] 4.000 Help Bal.* OK

* only appears if a balance

has been defined.

When starting a sample series, the parameters that have been set to “Re- quest” in the method, are asked for. The entries are stored with <F3>,

“OK” and the display for the next sample (#...) appears. Pressing <F2>, “Start”, starts the sample series even if the sample data have not all been

entered yet. By pressing <F3>, “Sample” during a titration, the state (ready, active,

done) of the samples is displayed. Pressing <F2>, “Modify”, allows you to change the entries or to complete them respectively. After each sample, the results are calculated and recorded, and the series is continued without displaying the results. If a printer is installed, the results are printed after each sample.

At the end of a series, the results of the last sample and the statistics for the series (press <F1>, “x”) are displayed. In the standby mode, the results can be viewed by pressing the <Results> key.

Important Results and statistics of a series are automatically deleted at

the start of the next series as soon as the message “Series aborted!” has been confirmed with <F3>, “OK”.

Note

• If an analysis has been terminated by the termination parameter “Max. time”, even though water has been detected in the

measuring cell of the coulometer, the sample rack is returned to its base position (position “Drift” is below the oven) and remains there even during pretitration for the next sample. Stromboli only changes to the next sample, when the DL39 goes into the standby mode.

• As soon as a Stromboli connected to the DL39 is switched on, any titration will start automatically, regardless of whether

“Autostart” “Yes” or “No” was selected. Therefore, the Stromboli must be switched off for a KF method with “Autostart...No” and

without a Stromboli.

• When using automatic sample determination with Stromboli, the coulometer only starts running the timer when the sample

has reached the set temperature.

• In the following cases, the sample series is interrupted. The message has to be confirmed by pressing <F3>, “OK” on the

titrator in order to continue the sample series.

• Appearance of one of the following messages: “Weight [g] 0”, “No titration!”, “Capacity exhausted”.

• The calculated value of “srel” is above the value entered in the method.

• Sampling and entering of the parameters pertaining to the sample take more than 5 minutes.

44 METTLER TOLEDO DL32/DL39

Auxiliary Functions (Stirrer, Pump, Results)

7 Auxiliary Functions (Stirrer, Pump, Results)

With the auxiliary functions keys, you can access menus that allow you to execute functions that are independent of a titration method, but support or expand it. While an analysis is running, all auxiliary functions are blocked: in standby mode you can activate only the functions of the <Stirrer> or <Results> keys.

7.1 Stirrer

You can switch the stirrer on and off and change its speed.

Stirrer STIRRER

Speed [%] 40

Start

The stirrer stirs at the defined speed.

To change the speed in the standby mode during a titration, – press the <Stirrer> key and change the speed.

Stirring can be started and stopped by pressing <F3>, “Start” or “Stop”.

Stirrer STIRRER

Speed [%] 35

– Confirm with <F3>, “OK”.

The stirrer stirs at the new speed.

– Press the <Run> key to return to the “Analysis” menu.

7.2 Pump

With the aid of the pump, you can empty the anodic and cathodic compartments.

Pump PUMP To empty, press <F3> To fill, press <F3>

and press and hold

blue pump button

Start

METTLER TOLEDO DL32/DL39 45

The pump is switched on or off by pressing <F3>, “Start” or “Stop”. While the pump is running, you can switch on the stirrer with <F2>, “Stir”.

Auxiliary Functions (Stirrer, Pump, Results)

Emptying

– Connect the silicon tubing from the top of the waste bottle to the pump inlet (back of the titrator) of the

pump unit.

– Push the waste tube of the waste bottle to the bottom of the cell. – Press <F3>, “Start”, and empty the cell. – Pull the waste tube out of the cell while the pump is still running. Repeat for cathodic chamber if

generation electrode with diaphragm is being used.

– Press <F3>, “Stop”. – Empty the waste bottle when full.

Note

• The pump will switch off automatically when the pumping time defined in the “Setup” menu has run out.

• Each pumping operation resets the electrolyte capacity to the value defined in the “Setup” menu.

7.3 Results

the following functions are available in this menu:

All results Recalculation Calculations (DL39 only) Statistics (DL39 only) Report Statistics series (DL39 only)

“All results“ is accessible when at least one result is available. “Statistics” are accessible when at least two results of a sample series are available. “Report” is accessible when a drift determination has been performed or a result is available. “Statistics series” is accessible when the first result of a sample series is available.

In order to change, e.g., results of KF determinations in the standby mode,

– press the <Results> key, change the result under “Recalculation” and confirm with “OK”. – press the <Run> key to return to the “Analysis” menu.

7.3.1 All results

You can view the results generated in the titration of a sample or sample series. You can also print out the results. The data in the result memory is deleted when you switch off the coulometer.

46 METTLER TOLEDO DL32/DL39

Auxiliary Functions (Stirrer, Pump, Results)

DL32 The results of the last 20 determinations are stored. DL39 You can perform a sample series with 99 samples. The results of the last 60 samples remain

stored, i.e., the results of sample 1 are deleted when you start to titrate sample 61. Calculations of statistical data is always based on the last 60 samples.

Note

• Samples terminated with the error message “No titration!” are also stored.

• The result of a determination you terminated with <Reset> is also stored.

7.3.2 Recalculation

You can recalculate existing results by changing the following values for each sample:

• in a KF sample determination: Drift, blank value and/or amount of sample.

• in a bromine index determination: Blank value and/or amount of sample.

Recalculn RESULTS Method 22 Sample 1 R1 : 105.1 ppm Sample 2

Modify OK

▼

Recalculn RESULTS Sample 1 Drift [µg/min] 6 Blank [µg] 0 Weight [g] 0.2 Undo OK

Recalculn RESULTS Method 22 *Sample 1 R1 : 105.1 ppm Sample 2

Modify OK

If you change one of the values, you can nullify it with <F1>, “Undo”. With “Undo”, the changed values are always reset to the original values.

The sample with the changed result is marked by an asterisk (*).

▼

METTLER TOLEDO DL32/DL39 47

Auxiliary Functions (Stirrer, Pump, Results)

Note

•

The values obtained in the determination always remain stored so that you can also nullify changes later.

• Under “All results” you can print out the recalculated results. The changed and the original values are

reported.

• DL39 The changed results are also taken into account for the statistical data.

7.3.3 Report

At the end of every determination, you can print out a (additional) data report or send it to the computer.

Report RESULTS

Output Print.+Comp. Type GLP

Help Modify Start

Note If you have changed the result of the last determination beforehand, it will be printed out marked

with an asterisk (*).

7.3.4 Calculations (DL39 only)

At the end of every titration, you can perform additional calculations for this sample.

Calculations RESULTS R = x [µg]*f

f = 1.0000 Unit µg Help Modify OK

With <F3>, “OK”, the result is displayed and can be printed out.

48 METTLER TOLEDO DL32/DL39

Auxiliary Functions (Stirrer, Pump, Results)

7.3.5 Statistics (DL39 only)

If you have selected “Statistics: Yes” in the method under calculation 1, 2 or 3, the mean is calculated in a series of 2 samples. For more than 2 samples the absolute and relative standard deviation are additionally calculated. You can print out these results here and modify the statistical evaluation by eliminating outliers.

In its statistical calculations the DL39 does not incorporate results that were obtained after a “Reset” or after the message “No titration!”.

Example of a statistical evaluation of 3 samples

Statistics RESULTS Method 22 R1 n = 3 x = 105.1 ppm s = 0.010912 Result Print OK

▼

Using the list of results, you decide which sample result is an outlier and then delete it.

Statistics RESULTS Method 22 Sample 1 R1 = 105.1 ppm Sample 2 Delete OK

Statistics RESULTS Method 22 R1 n = 2 x = 105.1 ppm

Result Print OK

If you delete “Sample 1” with <F1>, “Delete”, “Undo” is displayed to allow you to nullify the command. Simultaneously sample 1 is marked as “De- leted”.

By pressing <F3>, “OK”, the following appears:

▼

The statistical data based on the changed number of samples (e.g.: sample 1 is deleted) is calculated. You can delete several sample results and print out the statistics each time.

As long as the result list of this sample series is stored, you are able to nullify the deletion operation.

METTLER TOLEDO DL32/DL39 49

Auxiliary Functions (Stirrer, Pump, Results)

7.3.6 Statistics series (DL39 only)

With the help of this function you can terminate a sample series. This clears all data in the result memory. A subsequent analysis with the same method restarts with “Sample 1”.

Stat. series RESULTS End series? No Yes

50 METTLER TOLEDO DL32/DL39

Information Menu ( key)

8 Information Menu ( key)

The measured values and menus below are stored under the key:

Capacity [mg] 80 Drift [µg/min] 0 Blank [µg] 0 Hello! (Tutorial) Hardware tests

Capacity The anolyte capacity defined in the “Setup” menu is entered as an initial value. After each

titration, the difference between the initial value and the amount of analyzed water is displayed. If “0” is reached or exceeded, an error message appears.

Note As soon as you press the pump button, the value defined in the “Setup”

menu is reentered.

Drift The value of the last drift determination performed is stored here and automatically adopted

for the drift compensation if you have defined “Drift: Determination” as a method parameter.

Blank The value of the last blank determination performed is stored here and automatically

adopted for calculations (only for method with Stromboli).

Hello! In this tutorial, you can acquaint yourself with the coulometer step by step. Hardware tests Here, there are functions at your disposal allowing you to test the hardware of the cou-

lometer. For these tests you need the connector set (see optional equipment).

METTLER TOLEDO DL32/DL39 51

Error Messages and Malfunctions

9 Error Messages and Malfunctions

9.1 Error messages from the coulometer

Error messages that refer to this section or that are not self-explanatory are explained here.

A. After the coulometer has been switched on, the following errors could be displayed

• ERROR

• RAM x test ERROR(Q)“x” represents a number

• ERROR –> HW version

• ERROR –> DCB

• ERROR –> application

• No application found

The messages refer to a faulty hardware component. – Press any key: The coulometer attempts to continue the booting procedure; this may be successful, but

it does not guarantee proper functioning.

Measures

– Note the displayed text. – Note the serial number and software version (can be found on every report). – Notify METTLER TOLEDO Service of these points as well as of the attached peripheral units and the

defined configuration.

B. If the following three displays appear, parts of your hardware may be defective

Internal error: x

xxxxxxxxxxxxxxxxxxxxxxxxx xxxxxxxxxxxxxxxxxxxxxxxxx xxxxxxxxxxxxxxxxxxxxxxxxx SYSTEM IS BLOCKED! See manual: Errors

ERROR: x

SYSTEM IS BLOCKED! Please call METTLER TOLEDO service

OS ERROR: x P1: xx P2: xx D1: xx D2: xx SYSTEM IS BLOCKED! Please call METTLER TOLEDO service

“x” represents letters and/or

numbers

Measure

– Apart from the text or error (e.g., “ERROR: 1000), also note the procedure that triggered the error. – Note the serial number and software version (can be found on every report). – Switch off the coulometer. – Notify METTLER TOLEDO Service of these points as well as of the attached peripheral units and the

defined configuration.

52 METTLER TOLEDO DL32/DL39

Error Messages and Malfunctions

If the following warning appears, you have to consider the current procedure as failed and repeat it

Warning: x

“x” represents a number

Press any key to continue

Measures

– Press any key: The coulometer can continue to function. – On no account consider the result of a determination terminated in this manner! – Should the warning appear frequently, take the measures mentioned under point B.

D. Faulty data deleted!

• The coulometer has only saved parts of a method if, e.g., the power fails while the method is being saved. This will delete the method completely. It also possible that several methods have been deleted.

Measures

– Confirm the message. – Check which methods have been deleted and re-enter them.

• The coulometer has only saved parts of the parameters of a resource if, e.g., the power fails while the parameters are being saved. All data defined in the “Setup” menu will be deleted.

Measures

– Confirm the message. The coulometer then loads the default parameters of the “Setup” menu, i.e., all the

data that was stored on delivery.

– Switch the coulometer off and then on again. – Check whether the default parameters are active again. Re-enter the names and values saved before the

power failure.

If you receive this error message frequently, the battery is discharged! The battery must be changed by METTLER TOLEDO Service.

E. Method not stored!

• The coulometer can no longer save a method if the user data memory is full.

Measures

– Confirm the message. – Delete one or more unused methods. – Reenter the new method and save it.

METTLER TOLEDO DL32/DL39 53

Error Messages and Malfunctions

9.2 Other errors and malfunctions

The following collection of errors and malfunctions that are not reported by the coulometer will help you correct the fault yourself in many cases so that you do not have to rely on the METTLER TOLEDO Service (referred to in the table as “Service”).

You can also check some malfunctions with the hardware test (“Information” menu, key) first before you contact Service.

Error Possible cause Remedy

No display on Device not connected Connect to power supply, coulometer to power supply. otherwise, contact Service.

Several points on the Contact Service. display are missing

Display and keys Contact Service. do not match

Transmission error Peripheral device defective Check attached devices to attached or switched off. for correct functioning. peripheral device

Device (printer, Device not switched on Switch on device; balance, computer) wrong settings and/or settings and does not respond configuration (switch configuration must

positions wrong); match; wrong cable. check cable.

Pump does not Suction tube not Connect suction work connected; tube and check

connections;

defective pump. check pump.

TTL inputs or outputs Defective inputs. Check inputs/outputs. do not function

Magnetic stirring bar Cable of magnetic Check magnetic stirrer, does not rotate stirrer not plugged in change magnetic stirrer;

properly; wrong magnetic Use delivered magnetic stirring bar. stirring bar.

No hydrogen production Missing or bad Check contacts or at the generator electrode contacts; connectors call Service; check

interchanged. connectors (colors!).

“Conductivity too low! Current pulse of generator Confirm message with <F3> Titration terminated” electrode < 200 mA (instrument performs a “Reset”)

54 METTLER TOLEDO DL32/DL39

Error Messages and Malfunctions

9.3 Checking hardware

The menu “Hardware tests” is stored under the key and you can use it to check whether, e.g., the stirrer and pump of the coulometer are functioning correctly. If you order the connector set for the interface check, you can also test the interface and the TTL input and outputs of the coulometer

9.3.1 User interface

Display test

Five displays appear in succession, four with different patterns, the last without a pattern. This allows you to detect faulty pixels on the display. The test mode automatically switches off after approx. 20 seconds.

Keyboard test

When you press a key, a numeric code assigned to this key appears. This allows you to recognize a faulty key (see following table).

– Press the <Esc> key to quit the test mode.

Key codes

Key ............Code Key ............. Code Key ............. Code

Reset ..........23 F1 ............... 17 3................. 3

i .................30 F2 ............... 18 4................. 4

Stirrer..........28 F3 ............... 19 5................. 5

Pump .........27 ∇................ 11 6 ................. 6

Burette ........29 ∆ ................ 12 7 ................. 7

Results ....... 26 Shift ............ 10 8................. 8

Setup ..........25 0 ................ 0 9 ................. 9

Method .......24 1 ................ 1 Del .............. 31

Run ............21 2 ................ 2 ................... 33

Beep test

used to test the internal beeper

9.3.2 Peripheral interfaces

Interface test

– Before the test

• plug the test plug 51107288 into the balance, computer or GA42 interface.

• plug the Centronics cable into the Centronics interface and the test plug 51107287 into the Centronics

socket of the cable.

After the testing phase, either “Test successful” or “Test failed” will appear.

METTLER TOLEDO DL32/DL39 55

Error Messages and Malfunctions

Balance test

This menu option is not displayed if no balance is defined in the “Setup” menu. – The weight displayed on the balance must appear on the coulometer display.

Printer test (GA42, EPSON or HP)

The appropriate printer must be attached. If the error message “Printer: No connection” appears, you can quit this error message with <Esc>. With “OK” the coulometer tries to set up the connection to the printer again.

– The letters and characters available in the coulometer must be printed out.

9.3.3 Inputs and outputs TTL I/O (DL39 only)

– Before the test, connect the test plug 51107723 to the TTL I/O interface. After the testing phase, either “Test successful” or “Test failed” appears.

Internal stirrer

Here, you test the rotational movement (counterclockwise) and change in the speed of the magnetic stirring bar.

External stirrer

Here, you test the rotational movement and change in the speed of the magnetic stirring bar on the connected DV705 titration stand.

Internal pump

To test whether the pump functions.

– A “noise” must be heard. – It must be able to siphon off when the waste bottle is attached properly.

External pump

To test whether the pump on the optional external DV705 titration stand functions (see “Internal pump”). Note Always press the upper key (⇑ arrow) to siphon off.

56 METTLER TOLEDO DL32/DL39

Installation and Maintenance

10 Installation and Maintenance

10.1 Equipping the titration stand

After setting up your coulometer in an appropriate location you can equip the titration stand. The arm of the titrator can be turned in both directions.

– Carefully slide the magnetic stirring bar included in the delivery into the cell.

Note Only the original magnetic stirring bar will guarantee the specifications of your coulometer’s

magnetic stirrer.

– Place the cell in the titration stand and fasten it with the screw. – Grease the ground joints with the included grease (see delivery note). – Place the sample stopper with the septum into the opening in the cell. – Place the measuring and generator electrodes in their respective openings in the cell. – Fill the drying tube with desiccant and place it in the generator electrode. – Insert the holder for the tip of the waste bottle.

Measuring electrode

Septum

Sample stopper

Magnetic stirrer bar

Drying tube

Generator electrode

Holder for suction tube

Screw

Titration arm

METTLER TOLEDO DL32/DL39 57

Installation and Maintenance

10.2 Installing the waste bottle

Install the waste bottle to empty the cell (included in the delivery) as follows: – Push the suction tube tip first from underneath through the collar of the screw cap and place the tip into

the holder for the suction tube on the titration stand.

– Place the flat gasket on the waste bottle and screw on the screw cap. – Slide the silicone tube onto the drying tube of the bottle, connect the other end to the suction fitting on the

rear of the coulometer.

Suction tube

Silicon tube

Holder for suction tube

Drying tube

Screw cap

Flat gasket

Output

fitting

Suction

fitting

Notes

• You can connect a tube to the output fitting in order to carry solvent fumes to a suitable place.

• Check all connections for a tight fit in order to ensure the system’s tightness.

58 METTLER TOLEDO DL32/DL39

Installation and Maintenance

10.3 Attaching the magnetic stirrer, electrodes and devices

– Attach the devices used to the corresponding connectors/sockets on the rear side of the coulometer (see

diagram).

Measuring electrode (Sensor)

External titration stand (DV705)

Cooling ribs

Generator electrode

Stirrer

Waste bottle

(Suction fitting)

–

The stirrer output is not inherently short-circuit proof! Damaged pins of the cable connector

Pump unit

External power

pack

GA42 printer (RS-232C) Balance (RS-232C)

Computer (RS-232C) Oven (TTL I/O)

EPSON- or HP-compatible printer (Centronics)

On/Off switch

could cause a short circuit that will damage the coulometer, rendering it useless.

Magnetic stirrer

On delivery, the magnetic stirrer is pushed into the casing on the upper side of the coulometer.

– Attach its cable to the stirrer output. The arrow on the miniDIN connector must

point towards the screw.

Measuring electrode

– Connect the electrode to the triaxial cable. Plug the cable into the measuring electrode input (Sensor)

and insert the electrode into the top of the cell.

Generator electrode

– Connect the electrode to the triaxial cable. Plug the cable into the generator electrode input and insert the

generator electrode into the top of the cell.

Balance, printer, computer, TBox DR42

Attach all peripheral devices to the same plug connector (phase) to which the coulometer is connected! Otherwise, equalizing currents could flow across the cables.

METTLER TOLEDO and SARTORIUS balances are compatible with these coulometers.

METTLER TOLEDO DL32/DL39 59

Installation and Maintenance

10.4 Maintenance and servicing

All Karl-Fischer reagents are easily combustible and poisonous.

- In the case of skin contact, rinse immediately with a lot of water.

- In the case of eye contact, rinse immediately and thoroughly with water, then consult a doctor.

Cleaning

– You can clean the coulometer with a cloth moistened with alcohol – If necessary, grease ground joints.

Clean the cell as follows

– Empty the anode and cathode compartments using the waste bottle and pump. – Rinse thoroughly with methanol. Persistent contamination can be removed by using a common cleanser

(cleanser for lab equipment).

– Dry with a lint-free cloth. – Dry in drying oven over night at 70 - 80 °C. – If necessary, grease ground joints.

Clean the measuring and generator electrode as follows

– Rinse thoroughly with methanol. – Dry with a lint-free cloth. – In case of a contaminated diaphragm:

– Over night, soak the electrode in a suitable solution (preferably methanol). – Dry in the drying oven at 70 - 80 °C. – An electrochemical cleaning of the electrodes can be performed as follows:

– Fill the generator electrode with methanol and place it in a vessel filled with methanol. Connect the

generator electrode to a DC power source of 30 V / 1 A (if available, use a lab power pack with 30 V / 2 A).

– Reverse the polarity of the current after 5 minutes and permit it to react for another 5 minutes. – Rinse well with methanol and dry in the drying oven at 70 – 80 °C for several hours.

Note Use of a fritt cleanser is not recommended.

Waste bottle

– The tubing should be replaced when the Teflon seal no longer seals properly (wear and tear).

Molecular sieve

– If the drift remains too high you should fill the drying tubes with fresh molecular sieve.

Note You can regenerate molecular sieve in a drying oven at 160 - 300 °C for at least 24 hours.

60 METTLER TOLEDO DL32/DL39

Installation and Maintenance

Pump unit

If the diaphragm pump no longer functions, you can replace it: – Pull out the pump unit and insert the new one.

Magnetic stirrer

If the magnetic stirrer is defective, you can replace it:

Battery

The battery installed in the coulometer has a service life of approx. 5 years. The battery may be changed only by METTLER TOLEDO Service.

Disposal

Contact your METTLER TOLEDO dealer if you have to dispose of the coulometer.

10.5 Using TTL inputs and outputs (DL39 only)

You can only connect the METTLER TOLEDO oven sample changer Stromboli to this TTL socket.

METTLER TOLEDO DL32/DL39 61

62 METTLER TOLEDO DL32/DL39

Standard and optional equipment

11 Standard and optional equipment

You can order each part listed with an order number from METTLER TOLEDO.

11.1 Standard equipment

Coulometer

Titration cell

51108732

Magnetic stirrer

51108750

Magnetic stirrer bar

51191159

External power pack 100 - 240 VAC

51107777

Sample stopper (PTFE) with septum

51108741

Septum (12 pieces)

51108740

Brown glass bottle 1L

71296

Gasket

23981

Screw cap

23937

Pump unit

51107479

Fastener screw for titration cell (PTFE)

51108752

Pump button (blue)

51107600

METTLER TOLEDO DL32/DL39 63

Silicon tube Length: 0.45 m

51107490

Suction tube (PTFE) Length: 0.8 m

23936

Holder

23960

Standard and optional equipment

Keypad cover 1 piece

Seal (drying tube of titration stand)

51107492

Drying tube with cover

23961

Bottle with molecular sieve

71478

Silicon grease

71300

Measuring electrode DM143-SC (double platinum pin electrode)

51107699

Cable for DM143-SC (LEMO - SC) Length: 0.6 m

89601

Cable for generator electrode

51107830

Syringe, 1 piece

Injection needle (80 x 0.8 mm), 1 piece

Bedienungsanleitung

Operating Instructions German 51710107 English 51710108

KF-Coulometer

DL32 / DL39

French 51710109 Spanish 51710110

Die 4 wichtigsten Schritte

Setup

Method

Run

Results

–Das Coulometer mit den entsprechen-

den Hilfsmitteln einrichten.

Hauptmethoden (nur DL39) Peripherie Einstellungen

–Eine Methode wählen und nach Bedarf

ändern.

Benutzermethoden (nur DL39) METTLER-Methoden (nur DL39)

911 Standard 1.0 912 Stromboli 913 Ext.Extr. 914 Br Index 915 Br Blank

KF-Standardmethode

–Analyse mit der gewählten Methode star-

ten, indem Sie <Run> oder <F3>, „Probe“, drücken.

–Abfragen beantworten. –Probe zugeben. (DL39: Falls „Autostart:

Ja“ gewählt wurde, beginnt die Titration automatisch bereits nach Zugabe der Probe.)

–<Run> oder <F3>, „Start“, drücken, um

die Analyse zu starten. (DL39: Falls „Autostart: Ja“ gewählt wurde, entfällt dieser Schritt.)

–Resultatliste von analysierten Proben

anschauen, Nachberechnungen durchführen, die statistische Auswertung einer Serie ändern (nur DL39!) sowie zusätzliche Protokolle ausdrucken.

Die KF-Standardmethode

Nr. der Methode 0 Titel der Methode Probenparameter

ID Art Masse Minimum [g] 0.0000 Maximum [g] 5.0000 Eingabe Vorher

Drehzahl [%] 40 Mischzeit [s] 10

→→

Autostart Nein

→ nur DL39 →→

Regelparameter

Pol.-Strom [∝A] 2 Endpunkt [mV] 100 Erz.-rate Normal

Abbruchparameter

Max. Zeit [s] 600 Driftstopp Rel. Drift [∝g/min] 5

∝

g] 0

Blindwert [ Drift Online

Autor der Methode

→→

Resultat

→ nur DL32 →→

Berechnung 1 ppm

R1 = x [ppm]*f1 f1 = 1.0000 Einheit ppm Dezimalstellen 2 Statistik Ja Max. srel [%] 0.00

Berechnung 2

R2 = Keine Berech. f2 = 1.0000

→→

Einheit

→ nur DL39 →→

Dezimalstellen 2 Statistik Ja Max. srel [%] 0.00

Berechnung 3

R3 = Keine Berech. f3 = 1.0000 Einheit Dezimalstellen 2 Statistik Ja Max. srel [%] 0.00

Standby Ja Protokoll

AusgabeDruck.+Comp. Typ GLP

Italian 51710111

DL32 D / DL39 D DL32 X / DL39 X

Generator electrode with diaphragm

with straight

drying tube

51108751

11.2 Optional equipment

Drying oven

DO307

P O W

E R

T E M P

E R A T U

R E

H E A T I N G

0 2 0

0 1 0 0

0 8 0

0 6 0

0 4 0

2 6

0 O F F

2 8

0 3 0 0

Adaptor for DO307

51108761

Memo card German 51710112 English 51710113 French 51710114 Spanish 51710115 Italian 51710116

Generator electrode without diaphragm

with straight

drying tube

51108753

Oven sample changer Stromboli with DL39D or DL39X only

Stromboli

Connection cable for Stromboli (DL39 only)

51190589

64 METTLER TOLEDO DL32/DL39

Standard and optional equipment

Operating

Instructions

METTLER

TOLEDO

DL31/DL38:

Description

the

Computer

Interface

External titration stand

DV705

Connection cable for METTLER TOLEDO balance AM, PM, AT, AX

229029

Titration arm, without screw, without holder

51108729

Connection cable for METTLER TOLEDO balance AG, AB, PB, PG (LC interface)

229065

Waste bottle complete

51108745

Connection cable for METTLER TOLEDO balance AB, PB, PG-S (RS9 interface)

11101051

. 3

g . 3

1 9

g . 0

5 5

5 0

. 0

MET

9 7

g . 8

ER TO

2 0

1.0 g

8 g

GA42

Olivetti Artjet printer US version 51190986 EU version 51190985

Printer

Connection cable for METTLER TOLEDO balance AE with option 011

59759

Connection cable for SARTORIUS balances

51190363

Keypad cover 3 pieces

51107666

Connector set for hardware tests

51107790

Connection cable for GA42 printer

51190362

Connection cable for EPSON/HP compatible printer (i.e. Olivetti Artjet)

51107780

Syringe, 100 pieces 1 mL 71492 10 mL 71482

1 mL

Injection needle, 12 pieces 80 x 1.2 mm 71483

Operating

Instructions

METTLER

TOLEDO

DL31/DL38:

Description

the

Computer

Interface

80 x 0.8 mm 71484

Description of the interface German 51709875 English 51709876

Drying tube, bent, for DO307

51108639

Drying tube, straight,

51108733

METTLER TOLEDO DL32/DL39 65

Technical Data

12 Technical Data

Power supply (External power pack)

Voltages 100 – 240 VAC ± 10 % Frequency 50/60 Hz Power consumption 45 VA Fuse T3,15H250V (not interchangeable) Voltage 24 V 0,8 A / 5 V 1,2 A

Dimensions

Width 240 mm Depth 305 mm Height 370 mm Weight approx. 3.5 kg

Materials

Housing Polypropylene Titration stand Polypropylene Keypad Polyester Titration cell Glass Suction tube PTFE

Ambient conditions

Ambient temperature +5 °C ... +40 °C Atmospheric humidity max. 80 % at 40 °C Use indoors Overvoltage category II Pollution degree 2

Measurement system

KF input Triaxial socket Pol. current (Sensor) 1 µA, 2 µA or 5 µA End point 100 mV Generator current 60 mA, 100 mA, 200 mA, 400 mA (automatic steps) Generator voltage 28 V (pulsating) Max. permissible errors < 0.2 %

66 METTLER TOLEDO DL32/DL39

Outputs

Output 8-pin socket (mini DIN) Magnetic stirrer type Stepper motor Speed Software controlled (1–100%) Power 2 W (24 V) Max. speed 1050 rpm (40 % ≈ 600 rpm, 70 % ≈ 1050 rpm)

Output 5-pin socket (mini DIN) Magnetic stirrer type DC motor Speed Software controlled (1–100%) Voltage range 0 bis 18 VDC (max. 300 mA) Pump Voltage 24 VDC (max. 400 mA)

Technical Data

Magnetic stirrer (stepper motor)

Max. Speed 1050 rpm Power consumption 2 W

Diaphragm pump

Voltage 24 VAC (4 W) Pressure buildup approx. 150 mbar

Display

Liquid crystal display 6 lines, 20 characters per line,

backlit

Languages German, English, French,

Spanish, Italian and Russian

Memories

KF standard method 1 Tutorial method 1 METTLER methods 5 (DL39) User methods max. 50 (DL39) / max. 1 (DL32)

Interface

TTL I/O D-sub connector 9-pin

METTLER TOLEDO DL32/DL39 67

Technical Data

Attachment possibilities for peripherals

Balance Attachment via RS232C interface

(9-pin D-sub connector) for METTLER TOLEDO and SARTORIUS balances

Printer Attachment via RS232C interface

(9-pin D-sub connector) for GA42 printer Attachment via Centronics interface (25-pin D-sub socket) for commercial EPSON compatible printers with

parallel interface

Computer Attachment via RS232C interface

(9-pin D-sub connector): full-duplex, short-circuit-proof, handshake: X on/off, no hardware handshake

Stromboli Attachment via TTL I/O socket (9-pin D-sub)

RS232C connector (balance/GA42/computer)

RxD (In)

TxD (Out)

DTR GND

+12 V

470 Ω

Titrator

Data to coulometer

2 3

Data from coulometer

Handshake from coulometer fixed to operational readiness

Signal ground, galvanically connected to coulometer electronics

TTL I/O socket

In TTL; short-circuit-proof; Pulse ≥150 ms

IN1 IN2 OUT1 OUT2 OUT3 OUT4

GND

Titrator

1 2 3 4

Out Open collector

5 6 7 8

GND Signal ground, galvanically connected to coulometer elec-

(the input signal for the coulometer must be at least 150 ms)

• Vce max. = 24 V

• Ic max. = 20 mA

tronics

68 METTLER TOLEDO DL32/DL39

Centronics socket

Technical Data

13 12 11 10 9 8 7 6 5 4 3 2 1

25 24 23 22 21 20 19 18 17 16 15 14

\Strobe PD0 PD1 PD2 PD3 PD4 PD5 PD6 PD7 \ACK \BUSY PE SLCT \AUTOFDXT \ERROR \INIT \SLCTIN

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

Data ready

Data accepted Printer busy End of paper Printer aktive Automatic line feed Printer error Printer initialized Printer selected

Signal ground, galvanically connected to coulometer electronics

Coulometer

METTLER TOLEDO DL32/DL39 69

70 METTLER TOLEDO DL32/DL39

Index

Analysis 33 Anolyte 6 Application Brochure 5 Arrow keys 10 Auto start 23, 39 Auxiliary function keys 12 Auxiliary functions 45

Balance 16, 39, 59, 68 Battery 61 Beep 19 Blank 24, 30, 41, 51 Bromine 6 Bromine index 6, 29, 42

Calculation 24, 25, 39 Calculation formula 43 Calculations 48 Capacity 19, 51 Centronics 69 Cleaning 60 Command keys 10 Computer 17, 59, 68 Control parameters 23

Date 18 Density 22 Diaphragm 6 Display test 55 Disposal 61 Drift 24, 34, 41, 51 Drift compensation 39 Drift stop 23

Electrodes 59 Electrolyte 12 End point 23 Enter keys 12 Entry 22 Equipping the titration stand 57 ERROR 52 Error messages 52 Errors 54 Esc key 10 Expert 18, 75

Generator electrode 6, 17, 59

Hardware tests 51 Hello! 51

i key 11, 51 ID 22 Information menu 51 Inputs 56 Installation 57 Installing the waste bottle 58 Interfaces 55 Iodine 6

Keyboard test 55 KF standard method 20, 21

Language 13, 18

METTLER TOLEDO DL32/DL39 71

Index

Magnetic stirrer 59, 61 Main method 14 Maintenance 57, 60 Malfunctions 52, 54 Max. srel 25 Measuring electrode 6, 59 Menu keys 11 Method 20, 35 METTLER method 20, 28, 29 Mix time 22

Operating concept 9 Operation 9 Operational safety 7 Optional equipment 64 Outputs 56 Oven sample changer 17, 43

Peripherals 15 Pol. current 23 Post consumption 39 Pretitration 34 Principle of measurement 6 Printer 15, 59 Pump 45 Pump unit 61 Pumping time 19 Putting into operation 9

Recalculation 47 Report 25, 48 Reset key 11 Result 24 Results 35, 45, 46 Routine 19, 75 RS232C 68

Safety Measures 7 Sample changer 17, 43 Sample determination 36, 37 Sample parameter 22 Servicing 60 Settings 18 Setup 14 Speed 22, 35 Standard equipment 63 Standby 25 Standby mode 35 Starting a method 33 Statistics 25, 40, 49 Statistics series 50 Stirrer 12, 45 Storage procedures 26 Stromboli 17, 31, 43

TBox 59 Technical Data 66 Termination parameters 23 Time 18 Titration stand 16 Titrator ID 18 TTL I/O 56, 68 Tutorial 10 Type 22

User list 18 User method 11, 20, 28, 29

72 METTLER TOLEDO DL32/DL39

METTLER TOLEDO DL32/DL39 73

74 METTLER TOLEDO DL32/DL39

Switching from routine to expert mode

Settings SETUP Titrator ID Acces for Routine Beep Yes Solv. capac.[mL] 80 Help OK

Settings SETUP Titrator ID Acces for Routine Beep Yes Solv. capac.[mL] 80 Help Modify OK

▲

Select this line in the Setup menu. – While holding down the Shift key, press key 1 three times:

▼

▲

“Modify” is assigned to <F2> allowing you to select “Expert”.

▼

– Confirm with <F3>, “OK” to save the change.

METTLER TOLEDO DL32/DL39 75

✃

76 METTLER TOLEDO DL32/DL39

To protect your METTLER TOLEDO product’s future: METTLER TOLEDO Service assures the quality, measuring accuracy and preservation of value of all METTLER TOLEDO products for years to come. Please send for full details about our attractive terms of service. Thank you.

Printed on 100% chlorine-free paper, for the sake of our environment.

*P51710108*

Mettler-Toledo GmbH, Analytical, Sonnenbergstrasse 74, CH-8603 Schwerzenbach,

Tel. ++41 1 806 77 11, Fax ++41 1 806 73 50, Internet: http://www.mt.com

Subject to technical changes

Mettler Toledo DL32, DL39 Operating Instructions Manual

Specifications and Main Features

Frequently Asked Questions

User Manual

1 The KF-Coulometer DL32/DL39

1.1 Where can you find what information?

1.2 Coulometric determination of water - principle of measurement

2 Safety Measures

2.1 Measures for your protection

2.2 Measures for operational safety

3 The Coulometer

3.1 Putting into operation

3.2 The operating concept

3.2.1 The arrow keys

3.2.2 The command keys

3.2.3 The <Reset> key

3.2.4 The <i> key

3.2.5 The menu keys

3.2.6 The auxiliary function keys

3.2.7 The enter keys

3.3 Changing the language

4 Setup

4.1 Main methods (DL39 only)

4.2 Peripherals

4.2.1 Printer

4.2.2 Balance

4.2.3 Titration stand

4.2.4 Generator electrode

4.2.5 Computer

4.2.6 Oven sample changer Stromboli

4.3 Settings

5 Methods

5.1 The KF standard method

5.2 KF method parameters

5.2.1 No. (of the method)

5.2.2 Title (of the method)

5.2.3 Sample parameters ID You can enter an identification for the sample(s) now or just before the titration (“Request”)

5.2.4 Speed

5.2.5 Mix time

5.2.6 Auto start (DL39 only)

5.2.7 Control parameters

5.2.8 Termination parameters

5.2.9 Blank

5.2.10 Drift

5.2.11 Result (DL32 only)

5.2.12 Calculation 1 (DL39 only) R1 Result of the first calculation: The water content is calculated with the appropriate formula

5.2.13 Calculation 2 / Calculation 3 (DL39 only)

5.2.14 Standby

5.2.15 Report

5.2.16 Author of the method

5.3 Storage procedures

5.4 User and METTLER Methods (DL39 only)

5.5 METTLER methods “914 Br index” and “915 Br Blank” (DL39 only)

5.6 METTLER Method “912 Stromboli” (DL39 only)

6 Analysis (Run)

6.1 Starting a method

6.1.1 Menu sequence up to standby mode (KF methods)

6.1.2 Standby mode

6.2 Sample determination

6.2.1 Weight transfer from a balance

6.2.2 Post consumption

6.2.3 Calculations DL32 (without Auto start) / DL39 (“Auto start: No”)

6.2.4 Sample series with statistics (DL39 only)

6.3 Blank determination

6.4 Drift determination

6.5 Determination of bromine index (DL39 only)

6.6 Sample determination with the oven sample changer Stromboli (DL39 only)

7 Auxiliary Functions (Stirrer, Pump, Results)

7.1 Stirrer

7.2 Pump

7.3 Results

7.3.1 All results

7.3.2 Recalculation

7.3.3 Report

7.3.4 Calculations (DL39 only)

7.3.5 Statistics (DL39 only)

7.3.6 Statistics series (DL39 only)

8 Information Menu (<i> key)

9 Error Messages and Malfunctions

9.1 Error messages from the coulometer