##$K

Operating Instructions
METTLER TOLEDO Karl Fischer Titrator DL35

Notes and warnings for DL35 in compliance with IEC-348 and FCC A

Notes and warnings for DL35 in compliance with IEC-348 and FCC A
This instrument of protection class has been constructed and tested in compliance with
IEC publication 348, Safety Regulations for Electronic Measuring Instruments, and has
left the factory in faultless condition in regard to safety. To maintain this condition and
to ensure hazard-free operation, the user must observe the notes and warnings in
these operating instructions.
The instrument is intended for indoor use. It can be occasionally exposed to
temperatures between +50 C and -10 C without any adverse effects on its reliability.
Before switching on, ensure that the operating voltage set on the instrument matches
the power supply voltage.
If this instrument is to be operated using an autotransformer and a power supply of
higher voltage, it must be ensured that the base of the transformer is connected to the
neutral wire of the power supply.
The power connector may be inserted only in a socket with a ground contact. The
protective action must not be nullified by an extension lead without an equipment
grounding conductor.

DL35Manual
DL35
$
DL35 Operating Instructions
K
DL35 Operating Instructions
#

When covers are opened or parts removed, except where this is possible by hand, live
parts may be exposed. Connection points can also be live.
Before adjustment, servicing, corrective maintenance or replacement of parts, the
instruments must be disconnected from all voltage sources if it has to be opened.
It must be ensured that only fuses of the specified type and the specified rated
amperage are used as replacement. The use of repaired fuses or short circuiting of the
fuse holder is strictly forbidden.
If it appears that hazard-free operation is no longer possible, the instrument must be
shut down and secured against inadvertent usage.
It may be assumed that hazard-free operation is no longer possible
*
*
*
*

when the instrument shows signs of visible damage,

when the instrument no longer operates,
after lengthy storage under adverse conditions,
after severe transport stress.

Warning:
This equipment generates, uses, and can radiate radio frequency energy and if not
installed and used in accordance with the instructions manual, may cause interference
to radio communications. It has been tested and found to comply with the limits for a
Class A computing device pursuant to Subpart J of Part 15 of FCC Rules, which are
designed to provide reasonable protection against such interference when operated in
a commercial environment. Operation of this equipment in a residential area is likely to
cause interference in which case the user at his own expense will be required to take
whatever measures may be required to correct the interference.

Contents

Page

1.

Introduction

2.
2.1
2.2
2.3

Safety measures
Measures for your protection
Measures after accidents
Measures for operational safety

5
5
5
5

3.
3.1
3.2
3.3
3.4
3.5

Switching on the instrument

Entry of date and time
Filling the burette
Emptying the titration vessel
Changing the titration vessel
Dispensing the solvent

6
6
7
8
8
9

4.
4.1

The keypad
The functions of the individual keys

10
10

4.2

Key combinations with [RUN] and [MODE]

11

5.

Instrument parameters

13

6.
6.1
6.2
6.3
6.4
6.5
6.5.1
6.6
6.7

Methods
Parameters of the Karl Fischer methods
Developing a method
Storing a method
Selecting and modifying a method
Printing methods
Printing the list of methods
Deleting a method
METTLER methods

15
15
19
20
20
21
22
23
23

7.
7.1
7.2
7.3

Titration
Titration procedure
Total titrant consumption
Subsequent evaluation of results

25
25
28
29

8.
8.1
8.2
8.3
8.4

Statistical evaluation
Printing out statistics memory
Examining statistics data
Examining results memory, deleting individual results
Clearing statistics memory

31
32
33
34
36

9.
9.1
9.2
9.3

Titrant concentration CONC

Automatic determination
Entering CONC value manually
CONC determination with statistics

37
37
38
38

10.
10.1
10.2
10.3
10.4

DRIFT determination
Automatic determination
Entering DRIFT value manually
Continuous calculation of DRIFT during standby titration
Switch-off delay

39
39
39
40
40

11.

Blocking and unblocking of critical key functions

41

12.

Remote control

42

13.
13.1
13.2
13.3
13.3.1
13.3.2
13.3.3
13.3.4
13.3.5
13.3.6
13.3.7
13.4

Startup procedure
Checking the operating voltage
Changing the operating voltage
Setting up the instrument
Suction device
Dispensing device for the solvent
Attaching the pump
Installing the burette
Titration stand
Titration vessels
Magnetic stirrer
Peripheral devices

45
45
45
46
47
47
48
49
52
52
52
53

14.

Sample preparation

55

15.

Maintenance

57

16.

Technical data

59

17.
17.1
17.2

Accessories
Standard equipment
Optional accessories

60
60
62

18.
18.1
18.2
18.3
18.4

Malfunctions and their causes

Instrument malfunctions
Malfunctions in the communication with external devices
Operating errors
Other error conditions

67
67
67
67
67

19.

Description of the technical data for instruments conforming

to IEC-348

68

20.

Index

70

1.

Introduction

The titration of water by the Karl Fischer method is one of the most frequently used
methods for the determination of water. It allows water contents to be determined
reproducibly within 1 to 2 minutes over a wide concentration range (from a few ppm up
to 100%).
The Karl Fischer titration is based on the following principle:
Water reacts with iodine and a reactive component formed from the reaction of sulfur
dioxide with an alcohol (usually methanol) in the presence of a suitable base.
H2O + I2 + SO2 + 3RN -> [RNH]SO4CH3 + 2[RNH]I
RN = base
The essential requirements for a high titration quality are the rapid stoichiometric
reaction of water with the reagent, the free availability of the water being determined,
the absence of side reactions as well as due consideration of the ingress of extraneous
moisture into the titration system.
The Karl Fischer titration is indicated by a double platinum pin electrode with a constant
current applied across the pins. When the last traces of water have been titrated, the
measured potential falls to practically zero.
METTLER DL35 Karl Fischer Titrator
The new, compact METTLER DL35 Karl Fischer Titrator allows you to perform Karl
Fischer titrations simply, rapidly and reliably.
You can store 50 different methods. Ten of these are METTLER methods that are
already stored and can be called up immediately.
Pyridine-containing or pyridine-free one- or two-component Karl Fischer reagents can
be used with the DL35. The control algorithm is matched to modern, fast reacting Karl
Fischer reagents.

The drift due to moisture diffusing into the system can be determined in a simple
manner and is automatically taken into account in the results calculation.
The precharged solvent is automatically titrated to an anhydrous condition before the
titration. Between titrations, the system can be kept permanently anhydrous by a
standby titration.
You can transfer the sample weight before or after the titration directly from a balance.
Volumetric entries are converted automatically with the aid of the specified density
(specific weight).
If stirring has to be performed before the titration, the remaining stir time is continuously
displayed.
During a titration, you can obtain information on the current titrant consumption and
request an intermediate result calculated up to that particular time.
The potential change can be plotted on an attached analog line recorder.
The result printout includes not only the desired unit (mg, ppm, % or % dry weight), but
also other details such as the consumption of titrant in mL, the date and time of the
determination, the method used, etc.
Subsequent result evaluations with changed values of the drift, the concentration of the
titrant and the blank value are also possible.
After a titration, the subsequent consumption of titrant can be recorded; this provides
information on whether the sample is still releasing water.
Statistical evaluations are possible over several samples (including elimination of
outliers).
In order to check the supply of your titrant or to avoid exceeding the capacity of the
solvent, you can record the total titrant consumption.
This operating instructions apply to software version 1.0

References
K. Fischer, Angew. Chem. 48, 394 (1935)
J. Mitchell jr. and D.M. Smith
"Aquametry" Part III, 2. Auflage 1980
Verlag John Wiley & Sons, Inc, New York
HYDRANAL-Praktikum von Riedel-de Han
5. Auflage 1987
Seelze, Deutschland
G. Wieland
"Wasserbestimmung durch Karl-Fischer-Titration"
GIT Verlag GmbH, Darmstadt 1985
E. Scholz
"Karl-Fischer-Titration"
Springer Verlag Berlin 1984

2.

Safety measures

2.1

Measures for your protection

Before you start the titrations, please note the following rules:
All Karl Fischer reagents are highly inflammatory solutions. They are toxic. Do not
inhale! Do not swallow! Avoid skin contact!
When installing the burette, ensure that the burette tip is immersed and not in the air.
(Danger of splashing!)
Comply with all safety measures generally applicable in the lab!
2.2
Measures after accidents
After skin contact, immediately wash off with copious amounts of water!
After eye contact, immediately wash out thoroughly with copious amounts of water consult a doctor!
Note directions of the reagent manufacturers!
2.3
Measures for operational safety
For fault-free operation of the DL35, please note the following points:
Do not leave unreacted titrant in the titration vessel for lengthy periods since parts
made of silicon such as the septum and tubing connections of the suction tube can
be attacked.
If you do not switch on the instrument for more than 3 months, the battery will be
completely discharged and all stored data lost! The instrument must then be switched
on continuously for at least 72 hours to recharge the battery and reach operational
readiness.

3.

Switching on the instrument

Instrument startup is described in section 13.

3.1

Entry of date and time

8.8.8.8.8
When you switch on the instrument, all display segments light up
for control purposes for approx. 2 seconds.
SrSt

After this, the entire statistics memory is automatically cleared.

d.At

You can now confirm the date d.At or change it:

1 7 [RUN]

Enter the day, e.g. 17, confirm with [RUN].

dA.t O

8 [RUN]

Enter the month, e.g. 8, confirm with [RUN].

dAt.O

9 1 [RUN]

Enter the year, e.g. 91, confirm with [RUN].

You can enter 2 or 4 digits for the year; however, it will always be
outputted with 4 digits.

c.Lo O

You can now confirm the time c.Lo or change it:

Enter the hours, e.g. 15 (24-hour mode), confirm with [RUN].

1 5 [RUN]

cL.o O

3 1 [RUN]

Enter the minutes, e.g. 31, confirm with [RUN].

cLo. O

5 4 [RUN]

Enter the seconds, e.g. 54, confirm with [RUN].

The clock built into the instrument adopts your entry.

The DL35 is in the standby mode.

Notes
If you press the [RESET] key during the entry of the date or time, all values entered
up to that point are lost.
The time entry must always be in the 24-hour mode (hours-minutes-seconds),
irrespective of the time format selected (section 5, instrument parameter 2).
The date entry must always be in the European format (day-month-year), irrespective
of the date format selected (section 5, instrument parameter 3).
You can skip the date and time entry with the [RESET] key. The current values will
be automatically adopted when the instrument is switched on.
You can set the time display with the key sequence 12 [MODE]. Return to the
standby mode is effected with [RESET].
When in the standby mode you can change the date with 10 [MODE] or the time with
11 [MODE] at any time without first switching the instrument off.
In the case of a malfunction, you can set the date and time to zero with the key
sequence 91000 [MODE] and reenter them. You can call up this function only from
the standby mode.
Directly after switching on the instrument, you can clear the entire memory (methods
and statistics) with the key sequence 99999 [MODE]. At the same time, the 10
METTLER methods (Nos. 41-50) and the standard method (No. 0) are reloaded. The
date and time are set to 0 (zero), the default values are assigned to CONC and
DRIFT.
3.2
Filling the burette
If you press the [BURET/mL] key, the entire burette contents are discharged and fresh
titrant siphoned in. To ensure complete filling of the burette without air bubbles, you
should repeat this operation at least twice more.
3.3

Emptying the titration vessel

Siphoning off solution

Press the left button at the rear of the titration head with your left hand. This switches
on the pump. Use your right hand to position the suction tube in the solution so that
this is siphoned off. The suction tube should not quite reach the bottom of the
titration vessel.
With the pump still running, raise suction tube to the stop then release the button.
The pinch mechanism prevents subsequent flowback of liquid into the titration
vessel.
If you wish to stir the solution during siphon-ing off, first switch the stirrer on with 2
[RUN].
Warning
Do not leave unreacted titrant in the titration vessel for lengthy periods and always pull
up the suction tube to the stop since parts made of silicon such as the septum and
tubing connections of the suction tube can be attacked.
3.4

Changing the titration vessel

Remove titration vessel

Swing out titration head and undo fastener ring.
Attach the emptied or a clean, dry vessel.
3.5

Dispensing the solvent

Press the right button on the rear of the titration head with your right hand to switch
on the pump. When sufficient pressure has built up in the solvent bottle, solvent
starts to flow into the titration vessel.
Do not release the button until the two electrode tips and the burette tip are
immersed (min. 30 mL in a 150 mL beaker).

4.

The keypad

4.1
The functions of the individual keys
[RESET]
Aborts all operations. The instrument returns to the standby mode.
The display is set to zero and the burette filled if need be.
Use [RESET] to acknowledge an error message.
[CE]

Clears a wrongly entered number.

[DRIFT]

Displays the stored DRIFT value.

Manual entry of the DRIFT value: First enter the new value in
g/min, then press the [DRIFT] key.

[CONC]

Displays the stored CONC value.

Manual entry of the CONC value: First enter the new value in
mg/mL, then press the [CONC] key.

[RUN]

Initiates the following functions:

Start of a pretitration
Start of a titration, a CONC or DRIFT determination
Closing of entries
Skipping of displayed values (method parameters, results
memory, etc.)

[MODE]

Cyclic switching: From the standby mode (Karl Fischer titration

mode) via the CONC mode (concentration determination of the
titrant) to the DRIFT mode (DRIFT determination) and then back to
the standby mode. In the CONC and DRIFT mode, the lamps
above the corresponding keys light up.

n [SAVE]

Stores method n.

[METHOD]

Displays the number of the active method.

n [METHOD]

Method number n becomes the active method.

[BURET/mL]

The burette contents are discharged and the burette refilled. This
operation can be aborted by [RESET].

x [BURET/mL]

x mL titrant are dispensed.

Note
The volume of the burette used must match the burette volume
entered in the current method (method parameter B) in order for
the burette to dispense correctly.

4.2

Key combinations with [RUN] and [MODE]

Titration

1 [RUN]

Skip pretitration

2 [RUN]
4 [RUN]

Switch on stirrer
Subsequent result evaluation
Total titrant consumption

5 [RUN]

Display total titrant consumption

6 [RUN]

Set memory of total titrant consumption to 0 (zero)

DRIFT
7 [RUN]

Display current DRIFT during standby titration

8 [RUN]

Adopt current DRIFT (in DRIFT mode only)

Methods

0 [MODE]
1 [MODE]
2 [MODE]

Print out list of methods

Examine and change method parameters
Print out method parameters
Statistics

3 [MODE]

Examine or delete individual results

within 3 [MODE]:
n [RUN]: Display result of sample No. n
0 [RUN]: Delete current sample data

4 [MODE]
5 [MODE]
6 [MODE]

Examine statistics data

Print out statistics
Clear entire statistics memory (results and statistics data)
Instrument parameters

7 [MODE]

Examine or change instrument parameters

8 [MODE]
9 [MODE]

Print out instrument parameters

Abort subsequent consumption
Date/time

10 [MODE]

Change date

11 [MODE]
12 [MODE]

Change time
Display current time

18 [MODE]

Unblock critical functions

19 [MODE]

Block critical functions

Special functions

91000 [MODE]

Set date and time to zero

99999 [MODE]

Clear entire memory (methods and statistics). At the same time, the
10 METTLER methods (Nos. 41-50) and the standard method (No.
0) are reloaded. The date and time are set to 0 (zero). The default
values are assigned to CONC and DRIFT. You can only execute
these functions directly after the instrument has been switched on.

5.

Instrument parameters

You enter the input dialog for the instrument parameters by executing the key
sequence 7 [MODE]:

Parameter

Default value

Meaning

Instrument identification
0: No instrument identification.
n: Any identifier (max. 4 places), appears in the
header of the record.

Time format
0: European format (= 24-hour mode).
1: American format (= 12-hour mode).

Date format
0: European date entry (day-month-year).
1: American date entry (month-day-year).

Printer
0: No printer.
1: GA42 printer.
2: Epson-compatible dot matrix printer.

Total titrant consumption

0: The titrant consumption is not tracked.
n: Entry of the upper limit of the total titrant
consumption in mL.
Largest admissible value: 9999 mL.
If this limit is exceeded during operation,tltrL
appears on the display when you wish to start the
next titration; at the same time an audio signal is
sounded. The printer outputs "warning > titrant
limit". However, you can still start the titration with
[RUN]. You abort it with [RESET] and at the same
time the counter of the total titrant con-sumption is
set to 0 (zero); the display shows trSt and "titrant
reset" appears on the printed record.

You close these entries with [RESET].

You can print out the instrument parameters with the key sequence 8 [MODE].

6.

Methods

A method comprises all information needed to perform and evaluate a titration.

Maximum 50 methods can be stored in the DL35 and are identified by method numbers
(1-50). You can not delete the standard method (No. 0). But you can modify it and store
it under another number.
Methods 41-50 are the METTLER methods with the parameters for different Karl
Fischer titrations and concentration determinations. However, you can overwrite these
by your own methods.

6.1
Parameters of the Karl Fischer methods
The parameter numbers and letters have the following meaning:
Parameter

Default value

Meaning

15

Switch-off delay. The titration is at an end when the

measured signal remains constant for 15 seconds, i.e.
no dispensing of titrant is needed, the sample solution
is thus anhydrous. See also section 10.4.

41

Left digit:

Number of places following the

decimal point. Maximum 4 decimal
places can be selected. No entry is
interpreted as 0 places. The number of
the outputted decimal places can be less
than that entered if the size of the display
would lead to loss of places before the
decimal point.

Right digit:

Result unit:
0: mg

No request for sample weight.

1: %
For high water contents.
2: ppm For low water contents.
3: %dm Calculation of the dry content in
% (dry material): 100%-result% = %dm.
Note
In addition to the result in the desired unit, the titrant consumption in mL is always
specified on the record.
3

Reagent type
0: Pyridine-containing Karl Fischer reagent.
1: Pyridine-free one-component Karl Fischer reagent.
2: Pyridine-free Karl Fischer reagent and solvent.

Standard substance
0: Water.
1: Calibration standard with 5 mg water/mL.
2: Sodium tartrate 2H2O (standard substance with
15.66% water of crystallization).

Automatic standby titration

0: No standby titration. After the titration, the DL35

returns to the standby mode. A pretitration

automatically precedes the next titration. (Skipping
possible with the key sequence 1 [RUN].)
1: Standby titration. After the titration, the DL35
switches to the standby titration. Ingressing
moisture is con-tinuously removed by titration. The
next titration can be started at any time.
n: Subsequent consumption. After the pretitration
and after the titration, the DL35 switches to the
standby titration and prints out the subsequent
consumption at intervals of 1 minute over a period
of n minutes. During this time, the lamps "READY"
and "BUSY" are lit up.
When the configured time has elapsed, the DL35
remains in the standby titration mode ("READY"
lamp lit up). While the subsequent consumption is
being measured, a titration, a DRIFT or a
concentration determination can be started. The
other functions are blocked during this time. You
can
abort
the
subsequent
consumption
measurement prematurely with 9 [MODE]; the
standby titration continues to run.
6

Stir time request

0:
9999:
n:

9999:
n:

The DL35 requests the stir time

("STIRTIME") before every titration.
Fixed stir time in seconds before every
titration.

Blank value request

0:

No stir time.

No blank value.
Before every titration the DL35 requests
the blank value ("BLANK").
Fixed blank value in g water for every
titration.

Sample identification request

0:

No sample identification.

1:

Before every titration, the DL35 requests

the sample identification ("IDENT"). Default
value is always 0.
Before every titration, the DL35 expects
the sample identification; the previous
identifica-tion number appears as default
value.

2:

Audio signal
0:

No audio signal.

1:

Only the end of the titration and the

pretitration is signalled audibly.
Each keystroke, the end of every
pretitration and every titration are
acknowledged with an audio signal.

2:

50

Maximum titrant consumption

in mL per titration.

Burette volumein mL.

Statistics
0:

No statistical evaluation.

1:

Manual statistical evaluation; initiated with 5

[MODE]. (after max. 99 samples).
Automatic statistical evaluation after n titrations
(n = 2-99).

n:

Initial weight
0:

Weight entry before the titration.

1:

Weight entry after the titration, immediately before

calculation of the result.

Density
1:

g weighing: The density is not needed for the

titration.

x:

n:
x:

mL weighing: The DL35 expects a volume entry

on request of the sample weight (display voL).
With the density inputted here, it automatically
converts the volume entry into the corresponding
sample weight. The value of the density is
recorded.
whole number
fraction

6.2
Developing a method
When you switch the DL35 on for the first time in order to develop a method, the
standard method is recalled when in the standby mode with the key sequence 1
[MODE].
When the instrument is switched on the second, third time, etc., the last used method is

always active, even if it was a provisional one.

1 [MODE]

Call up of the input dialog.

The left digit shows the method parameter in question (e.g. 1:

Switch-off delay, see section 6.1). The digits on the right represent
the current value. You can overwrite or confirm this value.

l5

[RUN]

Press [RUN] to confirm the entry or the old value.

The next parameter appears on the display.

The entire parameter set can be run through repeatedly.
When you press the [RESET] key, the input dialog is concluded.

4l

[RESET]

If you have changed one or several parameters, you obtain a provisional method
without a method number. You can already perform titrations with a provisional method
and it is also preserved when the instrument is switched off. A provisional method
becomes definitive when it is assigned a number and stored.
Notes
If you can not enter the input dialog with 1 [MODE] from the standby mode, the
critical functions are blocked. You can unblock these with the key sequence 18
[MODE] (see section 11).
New parameter entries are immediately checked by the DL35 for validity. Invalid
entries are rejected with an audio signal and the old value redisplayed.
CONC and DRIFT are not part of a method. You yourself are responsible for the correctness of these values.
6.3
Storing a method
When you have selected the parameters for a method, you can give the method a
number and store it.
n [SAVE]
occ lO

[SAVE]

When in the standby mode, you store the method under method
number n (n=1-50) with this key sequence.
Appears on the display when a method is already stored under the
selected number, e.g. 10. Methods 41-50 are the METTLER
methods (see section 6.7). They can be overwritten.
If you press the [SAVE] key again, the old method is overwritten. If
you do not wish to overwrite the method, abort the operation with
[RESET] and store the new method under a different number.

Note
The current time and date are stored together with the method number. This allows
later versions of the same method to be distinguished from one another.
6.4
Selecting and modifying a method
n [METHOD]
When in the standby mode you can select the method number n
with this key sequence and use it for a titration. The method can
now also be examined, modified and printed out.

[METHOD]
no. lO

The current method, e.g. 10 is displayed as long as the [METHOD]

key
is pressed.

no.-

If you modify one or several parameters of the method, the method

becomes provisional. When this method is selected, the display
shows:
provisional method.
You can store the provisional method under the same or a different
number (see section 6.3).

6.5
Printing methods
2 [MODE]
With this key sequence you print out the current method when in
the standby mode.
Printout of the standard method

6.5.1
Printing the list of methods
0 [MODE]
When in the standby mode, this key sequence shows you a list of
the stored methods. Each method is accompanied by the method
number, the reagent type and the date and time of the last
modification.
With an Epson-compatible dot matrix printer (instrument parameter
4 has the value 2), you also obtain a printout of the following
method parameters: Switch-off delay; unit and number of decimal
places in the result; automatic standby titration; stir time; blank
value; burette volume; statistics.

6.6
Deleting a method
A method is deleted by overwriting it with method 0 (standard method).
Example: Method 25 should be deleted:
0 [METHOD]

Method 0 is activated.

25 [SAVE]

The activated method No. 0 should be stored as method 25.

occ 25

Method 25 is shown to be occupied.

[SAVE]

By pressing the [SAVE] key again, method 25 is overwritten by

method 0 and thus deleted.

Note
With 99999 [MODE] you have the possibility to clear the entire memory (methods and
statistics). At the same time, the 10 METTLER methods (Nos. 41-50) and the standard
method (No. 0) are reloaded. The date and time are set to 0 (zero). The default values
are assigned to CONC and DRIFT. This function can only be executed directly after the
instrument has been switched on.
6.7
METTLER methods
With the 10 METTLER methods you can perform different types of concentration and
water determinations without having to develop a method of your own. You will find
detailed information on how to perform these titrations in one of the METTLER
Application Bulletins (see section 17).
METTLER methods DL35 Karl Fischer Titrator
No. Designation
41 Concentration determination with the one-component reagent
Sample: sodium tartrate 2H2O (primary standard).
42

Concentration determination with the two-component reagent

Sample: sodium tartrate 2H2O.

43

Concentration determination with the one-component reagent

Sample: water.

44

Concentration determination with the two-component reagent

Sample: water.

45

Water determination in readily soluble samples, > 1% water content

Sample: cognac.

46

Water determination in slightly soluble samples, > 1% water content

Sample: butter.

47

Water determination in readily soluble samples, < 1% water content

Sample: toluene.

48

Water determination in slightly soluble samples, < 1% water content

Sample: edible oil.

49

Water determination in samples with external extraction, > 1% water content

Sample: coffee.

50

Water determination in samples with drying oven, < 1% water content

Sample: polyethylene granules.

7.

Titration

7.1
Titration procedure
The DL35 automatically performs a pretitration before every titration. The stirrer speed
must be matched to the volume of the solvent (pronounced vortex formation, but no air
bubbles). After the pretitration, the solvent is kept anhydrous (standby titration, possibly
with printout of subsequent consumption, see method parameter 5).
"READY" and "BUSY"
light up
or "READY" lights up

[RUN]

The instrument is ready for a titration, a DRIFT or a

CONC determination. If too much water enters the
vessel
(more than 6 DRIFT), "warning drift >" is printed out on
the record and the DL35 automatically starts a
pretitration again.
Start the titration with [RUN].
The DL35 starts to measure the time for the DRIFT
correction from this [RUN].
Add sample to titration vessel.
Now enter the values that the DL35 still needs for the
titration and the evaluation of the samples:

"WEIGHT" flashes

Weight entry: Enter weight in g. If a balance is

attached, the weight is automatically transferred.

At this point, the weight is requested only if you have

selected "weight entry before the titration" (method
parameter D), otherwise the weight is requested when
the titration is at an end.
If you have configured a density in the method
(parameter E, density different from 1.0), the DL35
expects a volume entry and voLO appears on the
display. An attached balance is not addressed.
[RUN]
"IDENT" flashes

Close weight entry with [RUN].

Enter sample identification.

[RUN]

Confirm with [RUN].

"STIRTIME" flashes

Enter stir time before the titration in seconds.

[RUN]

Confirm with [RUN].

"BLANK" flashes

Enter blank value in g.

[RUN]

Confirm with [RUN].

These three parameters are requested by the DL35
only if they have been defined in the method (method
parameters 6-8).
All entries are continuously printed out on the printer.

"BUSY" flashes
[RUN]
"BUSY" lights up

Start actual titration with [RUN].

The remaining stir time in seconds is continuously
displayed.
The titration runs.

Result

The result is displayed in the desired unit. The record

shows a printout of the titration time, the titrant
consumption and the result.

"READY" and "BUSY"

light up or

If you have configured an automatic standby titration,

the solution is kept anhydrous on completion of the
titration
and if configured (method parameter 5) the subsequent
consumption is printed out during the desired time
period.
Otherwise, the instrument returns to the standby mode.

"READY" lights up

Titration record:

Notes
With the key sequence 1 [RUN] it is possible to skip the pretitration. The solvent is
not titrated to dryness before sample addition, rather the total water in the titration
vessel is determined.
If you wait a long time before entering the weight after the titration, the subsequent
consumption can be drastically distorted since the instrument no longer exerts control
between the end of the titration and entry of the weight.
If a number is pressed during the titration, the intermediate result is shown for a brief
period. If the weight is not entered until after the titration, no calculation of the
intermediate result is possible. The display shows norES.
If the decimal point is pressed, the display shows the titrant consumption in mL. This
display disappears when the decimal point is pressed again.
The light bars on the display have the following meaning:
--.-.---.-. .
- . .

Burette dispenses or is being filled

Water still present
Last traces of water are being titrated
Solution anhydrous

If you have entered a value larger than 0 (zero) in instrument parameter 5, before
every titration and before the [BURET/mL] function a check is made to see if the
upper limit of the total titrant consumption has been exceeded. If yes, tltrL appears on
the display and the printer outputs "warning > titrant limit" (see section 7.2).
Fixed values specified in the method for the stir time and the blank value are not
shown on the result record. They can be found on the printout of the corresponding

method.
7.2
Total titrant consumption
In instrument parameter 5, you can set the upper limit of the total titrant consumption.
The total consumption of titrant is then continuously calculated over all titrations. You
can thus very easily ensure that the capacity of the precharged solvent is not
inadmissibly exceeded. You yourself define the value of the upper limit that has proved
suitable for your determinations. If this limit is exceeded, the display tltrL appears before
the start of the next titration and an audio signal sounds. "warning > titrant limit"
appears on the printed record. You can still start the titration with [RUN], with [RESET]
you abort the procedure and then you can change the solvent. The counter of the total
titrant consumption is automatically set to 0 (zero) in this case. The display shows trST,
and the printer outputs "titrant reset".
Display of the current total titrant consumption
5 [RUN]

When in the standby mode or the standby titration, you can display
the current total titrant consumption. The display disappears after
2-3 seconds. If you have selected 0 (zero) under instrument
parameter 5 (no tracking of the total titrant consumption), this
function is not active.
Zero setting of the total titrant consumption counter
6 [RUN]

You can reset the counter of the total titrant consumption to 0

(zero).
Changing the total titrant consumption
If you set a different upper limit in instrument parameter 5, the current value of the total
titrant consumption remains in force, it is not reset to 0 (zero).
If you change instrument parameter 5 from n to 0 (zero), i.e. you no longer wish to keep
track of the total titrant consumption, the counter is also set to 0 (zero).
Note
Both the pyridine-containing and the pyridine-free Karl Fischer reagents allow several
titrations to be performed in succession in the same solution. With unproblematic
samples (no interference by the matrix), the capacity (loading limit) is approx. 100 mg
H2O per 20 mL solvent. When the capacity limit is reached, the reaction rate slows and
the end of the titration is approached sluggishly.

7.3
Subsequent evaluation of results
On completion of a titration, you can perform a subsequent evaluation of the results
when in the standby mode by changing one or several of the values CONC, DRIFT and
BLANK:
4 [RUN]

Call up of the subsequent evaluation

"CONC"

CONC lamp lights up and the stored CONC value is displayed as a

suggestion. You can overwrite this value or confirm it directly with
[RUN].
DRIFT lamp lights up and the stored DRIFT value is displayed as a

"DRIFT"

"BLANK"

Result

suggestion. You can overwrite this value or confirm it directly with

[RUN].
BLANK lamp lights up and the stored BLANK value is displayed as
a suggestion. You can overwrite this value or confirm it directly with
[RUN].
The subsequent evaluation is now performed with the new values.
The values of DRIFT, CONC and BLANK are reset to the original
values after the calculation.

Notes
The subsequent evaluation can be performed only if a titration result is available (no
CONC or DRIFT determination).
If a determination of the subsequent consumption follows the titration, this must first
be allowed to run to completion or aborted with 9 [MODE].
The reevaluated results are not entered in the statistics!
Record of a subsequent evaluation

8.

Statistical evaluation

The DL35 has a statistics memory that comprises a results and a statistics data

memory. It allows the statistical evaluation of water and CONC determinations after a
series of maximum 99 samples with the same method.
The result of each sample is stored in the results memory. The sample number, the
weight and the result are stored for every sample.
The statistics data memory contains the number of samples, the mean value and the
absolute and relative standard deviation.
If you have selected 1 under method parameter C, you can generate and print out an
intermediate set of statistics after any number of titrations (n = 2-99) with 5 [MODE].
With 6 [MODE] you can clear the statistics memory and start a new series. Otherwise,
the next titration will continue the old series.
If you have entered a number (n = 2-99) under method parameter C, a set of statistics
will be automatically generated and printed out after n titrations. ( S out on the display,
"end of series" on the printed record.) When the next titration is started, the statistics
counter will be automatically reset to 1 and at the same time the statistics memory
cleared.
It is possible to delete the result of a sample from the results memory and to exclude it
from the statistical evaluation (see section 8.3). However, the storage location remains
occupied and the sample can thus not be repeated or substituted.
8.1
Printing out statistics memory
5 [MODE]
With this key sequence you can generate a set of statistics. The
mean value will be transferred if applicable (CONC determinations)
and the results recorded.
Printout of a set of statistics

Note
The DL35 calculates all results internally to 7 decimal places and does not round these
off to 4 places until the end. As a consequence, if you recalculate one of the results it
may deviate in the final decimal place from the result of the DL35.
8.2
Examining statistics data
4 [MODE]
With 4 [MODE] you can examine the current statistics data. If no
results are available, an audio signal sounds after 4 [MODE] and
the instrument returns to the standby mode.

A 1 appears on the display for approx. 1 second.

l
23

The number of samples is then indicated.

[RUN]

You obtain further information by pressing the [RUN] key:

A 2 appears on the display for approx. 1 second.

2
24.78

The mean value is then shown. The selected unit lights up at the
same time.

If only 1 result is stored, no standard deviation is calculated. In this case, [RUN] leads
first to the display of a 1, the information display then starts again from the beginning.
[RUN]

You obtain further information by pressing the [RUN] key:

A 3 appears on the display for approx. 1 second.

3
O.l8

The standard deviation is then shown. The selected unit lights up

at the same time.

[RUN]

You obtain further information by pressing the [RUN] key:

A 4 appears on the display for approx. 1 second.

4
l.79

The relative standard deviation is then shown in percent (percent

lamp lights up).

The statistics data memory can be run through again from the beginning with [RUN].
You can return to the standby mode with [RESET].
8.3

Examining results memory, deleting individual results

3 [MODE]
With the key sequence 3 [MODE] you can examine the results
memory and delete individual results. If the results memory is clear,
an audio signal sounds after 3 [MODE] and the instrument returns
to the standby mode.
The sample number lights up for approx. 1 second.

l
2.5555

The associated result then appears. The selected result unit (mg,
%, ppm or %dm) lights up at the same time.

[RUN]

By pressing the [RUN] key you are shown the next result.
The sample number lights up for approx. 1 second.

2
2.6754

The associated result then appears. The selected result unit (mg,
%, ppm or %dm) lights up at the same time.

n [RUN]

By pressing the key sequence n [RUN], you receive the result of

sample No. n directly.

To delete a result from the results memory, you must first select it then overwrite it with
0 [RUN]:
n [RUN]

You are shown the desired result directly.

The sample number, e.g. 10, lights up for approx. 1 second.

lO
2.4938

The associated result then appears. The selected result unit (mg,
%, ppm or %dm) lights up at the same time.

0 [RUN]

The result of the selected sample is deleted:

dEL

Display: dEL and automatic printout. The deleted sample is not

taken into account in the statistical evaluation.

[RUN]

By pressing the [RUN] key, you are shown the next result:
Sample number of the next sample, e.g. 11, lights up for approx. 1
second.

ll

2.4307

Result of the sample. The selected result unit (mg, %, ppm or

%dm) lights up at the same time.

Note
In CONC determinations, the unit mg and the CONC lamp both light up.
The results memory is quit with [RESET]; this has no influence on the statistics counter.
If a results memory contains deleted results, the corresponding statistics record will
show STATISTICS*. Deleted results are marked on the record with del.
Example of a statistics record with deleted results

Notes
With 6 [MODE] you can clear the entire statistics memory.
By pressing the [RUN] key, you can run through the results memory repeatedly.
8.4
Clearing statistics memory
6 [MODE]
Clears the entire statistics memory.
The entire statistics memory (all results and statistics data) is also cleared in the
following situations:
When the instrument is switched on (SrSt on the display, "statistics reset" on the
printed record).
When you modify at least one method parameter and hence create a provisional
method.
When the results memory is full (after 99 samples), "buffer full" appears on the
printer. The statistics are printed out and the memory cleared when the next titration
is started.
When the number of measurements entered for a set of statistics has been executed
(method parameter C>1), "end of series" appears on the printer. The statistics are
printed out and the memory cleared when the next titration is started.
Through a change in the stored CONC value by manual entry.
Through call up of a different method.
By switching from the CONC determination to titration or in the opposite direction: On
start of the measurement with [RUN], "mode changed" appears on the printed record,
the statistics are printed out, the mean value transferred if applicable (CONC
measurement series) and the statistics memory then cleared. If you have changed
the mode accidentally, you can abort with [RESET] while the DL35 is printing out the
statistics. The statistics memory has not yet been cleared and you can continue with
the next titration in the correct mode.
Notes
If the statistics memory has been cleared and data actually existed, SrSt appears on
the display and "statistics reset" on the printer.
Before the statistics memory is cleared, there is normally no printout of the statistics
memory.

9.

Titrant concentration CONC

The titrant concentration is stored in the DL35 as parameter CONC in mg water per mL
(standard value 5 mg H2O/mL). It should be determined daily with the aid of a standard
substance. For accurate titration results you should perform at least three concentration
determinations and evaluate these statistically. Note that the titrant concentration is not
part of the method.
The result of the CONC determination or the mean value of the statistics of a CONC
measurement series is stored directly in the DL35 for the evaluation of the subsequent
titrations.

9.1
Automatic determination
Press [MODE]: the lamp above the CONC key lights up. The DL35 is ready for a
concentration determination. It runs exactly as a normal titration (no blank inquiry).
A suitable amount of the defined standard substance is added as sample (see method
parameter 4):
Standard substance

Amount

Water

Water

0.005 - 0.02 g (5 - 20 L) with microliter syringe

100%

Standard substance
(5 mg H2O/mL)

1 - 4 mL with syringe or pipette

(In the weight request, voL appears on the
display: Enter amount of sample in mL!)

0.5%

Sodium tartrate, hydrate*

Add 0.05 - 0.15 g with weighing boat and

determine exact weight by differential weighing

15.66%

* Care: Never dry the primary standard substance in an oven! It would lose its water of
crystallization.
Note
If standard substances other than those recommended above are used, the calculated
amount of water in g can be entered in place of the sample weight (method parameter
4 has the value 0 (zero)).
9.2
Entering CONC value manually
If you wish to accept the titrant concentration specifications of the manufacturer, when
in the standby mode enter the value in mg water/mL and press the [CONC] key.
If the CONC value is manually overwritten, this change will be automatically recorded.
The statistics memory will then be automatically cleared.

9.3
CONC determination with statistics
If you perform several CONC determinations and wish to evaluate these statistically,
select under method parameter C
1:

n:

With 5 [MODE] you can generate and print out a set of statistics after any
number (2-99) of measurements. The calculated mean value is adopted as a
new CONC value. You can then continue the series or clear the statistics
memory with 6 [MODE] and start a new one.
After n samples, a set of statistics is generated and printed out automatically.
The calculated mean value is adopted as a new CONC value.

Between the individual determinations, the CONC value last determined is always
transferred to the CONC memory.
On completion of a CONC determination, the lamp above the [CONC] key does not go

out. The instrument remains in the CONC mode and is thus ready for the next CONC
determination.
Check on the stored CONC value:
Press the [CONC] key: The stored value is displayed.

10.

DRIFT determination

In solvent dried by titration a small titrant consumption can always be found and this is
primarily due to the diffusion of moisture into the vessel. This DRIFT is stored in the
DL35 as DRIFT value in g water per minute. The default value is 25 g/min and is
automatically taken into account in the result calculation. For accurate titrations and for
the determination of small amounts of water (<1 mg), you should determine the DRIFT
at regular intervals. Note that the DRIFT is not part of the method.

10.1
Automatic determination
Press [MODE] twice: The lamp above the DRIFT key lights up: The DL35 is ready for a
DRIFT determination.
If the solution in the vessel has not been dried by titration, a pretitration is first
performed. Depending on the titrant consumption, this is followed by a measurement
over a 3 - 5 minute period which is evaluated to a result with the first minute being
ignored. The result is printed out and stored directly in the DL35 for the evaluation of
subsequent titrations.
Check on the stored DRIFT value
Press the [DRIFT] key twice to display the stored DRIFT value.
10.2
Entering DRIFT value manually
In the standby mode, enter the value in g/min and press the DRIFT key.
The new DRIFT value is automatically recorded.
Notes
The experimentally determined DRIFT should be between 5 and 50 g/min. If the
value is too high, possible causes are:
- Titration head not closed properly.
- Drying agent on titration head no longer effective.
- Wetted areas are present on the underside of the titration head. Removal of the
water adsorbed at such sites by titration can take a very long time: remove titration
vessel and dry wetted areas.
- Samples that evolve water only slowly.
- Residual sample not determined by the titration still adhering to the wall of the
titration vessel.
After the DRIFT determination, you can check the subsequent consumption if you
configure "n" under method parameter 5.

 The DL35 starts to measure the time for the DRIFT correction in a titration after the
first [RUN].
10.3
Continuous calculation of DRIFT during standby titration
During the standby titration, the DRIFT is redetermined after every addition of titrant
and the mean value of the last 4 measurements calculated. With 7 [RUN] you can
display the current DRIFT and with 8 [RUN] transfer it in the DRIFT mode to the
memory. Pressing the DRIFT key displays the stored DRIFT value.
Note
The DL35 always uses the stored DRIFT in the result calculation.
10.4
Switch-off delay
The relationship between the switch-off delay, the DRIFT and the smallest increment of
titrant can be seen from the following formula:
smallest addition =
2 DRIFT switch-off delay / 60
g water
g/min
sec
sec/min
The DL35 sets the smallest increment of titrant to be dispensed so that it corresponds
to twice the DRIFT during the switch-off delay.
The following table shows how large the DRIFT may be at a particular burette volume
and a particular switch-off delay for the DL35 to titrate in the endpoint region with
maximum resolution (CONC = 5 mg/mL).

11.

Blocking and unblocking of critical key functions

If the same titrations have to be performed repeatedly, several functions of the DL35
can be blocked so that the methods can not be inadvertently changed. These functions
can be selected only when in the standby mode.
19 [MODE]

Blocking
Following functions are now blocked:

1 [MODE]

Examination

and

modification

of

the

method

7 [MODE]

Examination and modification of the instrument

parameters

parameters
10 [MODE]

Changing the date

11 [MODE]

Changing the time

91000 [MODE]

Setting the date and time to 0 (zero)

99999 [MODE]

Clearing the entire memory

x [CONC], x [DRIFT]
[MODE]

Overwriting of CONC and DRIFT

Determination of CONC and DRIFT

18 [MODE]

Unblocking
The above functions can now be used again.

12.

Remote control

The DL35 Karl Fischer Titrator can be fully remote controlled by a master control unit
(computer). All key functions can be controlled via the RS-232-C interface in
accordance with the below table.
Each remote control command causes blocking of the entire keypad since no provision
has been made for parallel operation. However, the keypad can be enabled by a
remote control command.
Key

Command

ASCII hex

0 to 9

0 to 9

30 to 39

2E

CE

43

RESET

47

BURET/mL

4B

RUN

48

MODE

49

DRIFT

4A

CONC

45

SAVE

4C

METHOD

4D

Release key (for DRIFT,

CONC, RUN)

5A

Unblock keypad

59

Simulated power switch-on

21

Status inquiry

3F

Mode inquiry

&

26

Display inquiry

23

Other characters are ignored.

Configuration of the interface:

Number data bits: 7

Baud rate: 2400
Parity: even

Stop bit: 1
The remote control commands do not produce an acknowledgment.
Exceptions
All printer outputs are also outputted simultaneously at the interface. Each printer
output is closed with the ASCII character CTRL Z (ASCII hex 1A).
Status, mode and display inquiry. The acknowledgement is an ASCII character
sequence and is closed with the two ASCII characters for carriage return (CR, ASCII
hex OD) and line feed (LF, ASCII hex OA).
Test of the interface
For testing the interface and becoming acquainted with the command set of the DL35
remote control, you can use either an ANSI terminal or a terminal program.
Example of a program in BASIC on an IBM-PC:
100 CM$="com1"
150 CLS: PRINT "Terminal Emulator"
160 OPEN CM$+":2400,e,7,1,cs0,ds0,cd0,pe" AS #1
170 T$=INKEY$
180 IF T$="" GOTO 210
190 IF ASC(T$)=27 THEN PRINT "Good bye": SYSTEM
200 PRINT T$;: PRINT #1,T$;
205 IF ASC (T$)=13 THEN PRINT CHR$ (10) ;
210 IF (256-LOF(1))=0 GOTO 170
220 P$=INPUT$ (1, #1)
230 IF ASC (P$)<>10 THEN PRINT P$;
235 IF ASC (P$)=13 THEN PRINT CHR$ (10) ;
240 GOTO 170
Status inquiry (?)
The status message shows the status of the operational guidance lamps on the left of
the display.
Lamp

Status

None

READY

flashing
WEIGHT

65
2

flashing

66

SAMPLE NO.

flashing

68

STIRTIME

flashing

72

BLANK

16

flashing
BUSY

80
32

flashing
READY and BUSY
all

96
33
63

Mode inquiry (&)

The mode message shows the status of the CONC and DRIFT lamps.
Lamp

Status

None

CONC
DRIFT

1
2

Display inquiry (#)

The display message shows the contents of the display as a character string. If a result
unit is active, this is appended at the end in clear text, e.g. "16.85 ppm".

13.

Startup procedure

13.1
Checking the operating voltage
Before switching on the instrument for the first time, check that the operating voltage
specifications on the yellow sticker (at power supply) match the power supply voltage of
the local supply.

13.2
Changing the operating voltage
Warning
Before you change the operating voltage, disconnect the power connector from the
power supply!

 Place instrument on the bench and undo the seven screws (1) using a Phillips
screwdriver.
Carefully loosen base from the top housing and lower it to the bench surface.
The transformer is built into the top housing.
Plug the cable (2) onto the spade connector marked with the local power supply
voltage.

When reassembling the instrument, make sure that the adjustment wheel for the
stirrer speed (3) lies in the slot provided for it in the top housing. If the RS-232-C data
output is installed, insert by pressing gently into the top housing. Reinsert and tighten the seven screws (1).
Lever out the fuse holder (arrow) between the on/off switch and connection to the
power supply using a screwdriver and check the rated current of the microfuse:
110/120 V 800 mA slow-blow*
230/240 V 400 mA slow-blow*
13.3

Setting up the instrument

Note
The accessories include two red and six white tubes:
2 double-walled, red tubes for the burette (17, 18)
2 single, white tubes for the suction device (7) and for solvent dispensing (10)
4 white tubes for air lines (19-22)
13.3.1 Suction device

 Insert suction tube (5) in titration head (6) and tighten with union nut (8).
Screw screw cap (4) (see illustration under 13.3) with gasket onto an empty brown
glass bottle and tighten well. Adapters are available for several bottle threads that do
not fit.
Push the free end of suction tube (7) through screw cap (4).
Fill drying tube (9) (see illustration under 13.3) with molecular sieves and mount on
screw cap (4). The molecular sieves protect the pump against acidic vapors of the
Karl Fischer solutions.
13.3.2 Dispensing device for the solvent

Insert solvent dispensing tube (10) in titration head (6) directly next to suction tube.
Screw screw cap (11) (see illustration under 13.3) with gasket onto the solvent bottle
and tighten well.
Push the free end of the solvent dispensing tube through screw cap (11) until it
touches the bottom of the bottle.
Fill drying tube (12) (see illustration under 13.3) with molecular sieves and mount on

screw cap (11).

Warning
Position the solvent bottle at the same height as the titrator; if the solvent bottle is
higher, solvent will run into the titration vessel until the levels are the same.
13.3.3 Attaching the pump

The pump (23) must be attached with the four white tubes (19-22) to the solvent and
suction bottles via the valve on the titration stand (24).
Plug in connector (25) of power supply cable below the electrode connectors.
The air vented during suction escapes through fitting (37) on titration stand (24) and
if need be can be led away by a tube to a suitable ventilation shaft.
Warning
The pump is attacked by the corrosive vapors of the Karl Fischer solvent and must
therefore be replaced after a certain time. If you change the molecular sieves
frequently, you prolong the service life of the pump.
13.3.4 Installing the burette
Assembly of the piston

a.

b.

Piston (1, 2 & 3) and piston rod (4) for a 10 mL or 20 mL burette:

Insert O-ring (1) in the groove in the lower part of piston (2) and screw together
with piston head (3) and piston rod (4).
Piston (1, 2 & 3) and piston rod (4) for a 5 mL burette.
Lay O-ring (1) in piston head (3); it does not slot into its final position until you
screw in piston rod (4) and the lower part of piston (2).

Inserting the piston

a.
b.

Carefully slide the piston into the burette cylinder so that the wider part of the
piston rod (1) remains visible.
Press the burette onto burette holder (2) thus positioning the piston exactly (3).

Fitting the burette

Turn the knurled arrestment wheel on the holder track of the DL35 to the right until it
reaches the stop. Move the burette on the holder track to the right until it snaps over
the drive. Turn the knurled arrestment wheel to the left and loosely tighten so that the
play between holder track and burette is taken up.

Equipping the burette

Lay flat gasket (2) on bottle (1) and screw on burette holder.
Insert drying tube holder (4a) with drying tube (4).
Note
If you do not have a bottle with thread DIN 168-GL 45 x 4 (order number 71296 or
Riedel-de Han bottle), you need an adapter appropriate to the bottle and a flat gasket
(see Accessories, section 17).
Warning
Always close the opening with a drying tube during titration. If you close the bottle with
a stopper, a partial vacuum forms.
Push suction tube (5) into the bottle - slide the red PE tube as kink protection over
fitting (5a) - and screw to left connection of burette head.
Screw dispensing tube (6) to right connection and place other end in tip holder (7).
(8) is the burette head that you can remove when cleaning the cylinder to avoid

smearing the inscription on sticker (9). (10) is the light protection tube.
If parts of the stopcock (11, 12, 13 & 14) have to be replaced, unscrew threaded ring
(11) and remove follower cam (12), rubber washer (13) and valve disk (14).
Place rubber washer (13) followed by valve disk (14) on follower cam (12). The cam
of the follower cam must be seated in the larger, oval hole of the valve disk.
Then lightly grease the surface of the valve disk with silicon grease.
Press the three parts from below onto the ceramic disk of the burette with the cam
(15) facing outward and center exactly. Pay particular attention to correct positioning
of slot (15), otherwise the burette could be damaged.
Invert the burette, mount threaded ring and screw on while holding the follower cam.
13.3.5 Titration stand

Insert electrode (14) into titration head (6) and attach to rear of instrument.
Fill drying tube (15) with molecular sieves and mount on titration head (6).
Insert burette dispensing tube (17) at titration head (6) to the left of the electrode:
The stirrer must move the titrant away from the electrode!
Insert glass stopper (16), septum or Karl Fischer stopper.
Place magnetic stirrer bar in titration vessel and fasten titration vessel with fastener
ring (38).
13.3.6 Titration vessels

You can install titration vessels of 150 mL or 250 mL or a thermostatable beaker. For
the 250 mL titration vessel you need a different fastener ring and must change the
height of the titration head:
Lift up titration head and swing to right until the stop.
Lift up titration head again and turn it further to the right until the next stop, raise it
and swing it back again.
Changeover to a 150 mL titration vessel is similar and involves lowering the titration
head in the rearmost position.
13.3.7 Magnetic stirrer
The DL35 has a magnetic stirrer with variable speed. It is located below the titration
stand. If you wish to switch on the stirrer, press 2 [RUN]. On the right of the DL35 is a
control knob for variable adjustment of the stirrer speed.
13.4

Peripheral devices

Methods and results can be recorded either with a Mettler-Toledo GA42 printer or an
Epson-compatible dot matrix printer (CL interface). The cable for the GA42 is enclosed.
The conversion cable for the dot matrix printer must be ordered separately (see section
17.2).
The dot matrix printer must have a serial interface with at least 2 KB buffer and which is
configured as follows:
Baud rate: 2400
Number data bits: 8
Parity: not checked

The DL35 also has an analog output for a line recorder.

If you attach a balance (e.g. Mettler-Toledo AT261), the DL35 automatically accepts the
sample weight. Appropriate connection cables are listed in section 17.2.
Warning
The data output of the attached balances must be configured as follows:
Baud rate: 2400
Parity: even
send continuous
These settings must be checked with the aid of the appropriate operating or mounting
instructions of the balance and corrected if necessary.

Attach printer and balance to the same interface.(The connector of the balance cable
has a socket that accepts the connector of the printer.)

An RS-232-C (DCE) data output for attachment of a computer (see section 12) can be
easily retrofitted to the DL35 Karl Fischer Titrator. The appropriate connection cable is
listed in section 17.2.

14.

Sample preparation

Aim:

The water contained in a sample should be freely available

for the titration.

Liquid samples

In general these need no sample preparation. With oils and

other samples poorly soluble in methanol, use a solvent
mixture. e.g. with chloroform.
Samples that react with components of the Karl Fischer
solutions (iodine, sulfur dioxide, alcohol) can cause
difficulties. This applies particularly to aldehydes, ketones,
carboxylic acids, thiols, and certain amines. They can usually
still be titrated if suitable measures are employed, e.g. special
titrants, buffers, etc.

Solid samples

The sample preparation depends on the solubility of the

samples in methanol or on the Karl Fischer solvent used and
the type of bonding of the water.
The following illustration shows a schematic representation of
how the total water is freely available in certain products
(curve a) and in other substances (curve b) partially free (III),
or moderately (II), poorly or not available at all (I).

Insoluble samples

Pulverize the sample using a ball mill, grater, mixer (e.g.

grain, coffee beans and many other foodstuffs).
Extraction of the sample with a suitable anhydrous solvent
(e.g. wood, paper).
Heating the sample in the Mettler-Toledo DO301 or DO302
Drying Oven and transfer of the evaporated water to the
titration vessel (e.g. certain plastics).

The Mettler-Toledo Application Brochures provide a detailed description of suitable

procedures for many applications (see section 17.2).
The simplest method to determine the weight is by differential weighing.
Place sample in a container (syringe, pipette, weighing boat, etc.) on the balance.
Tare the balance (set zero).
Transfer the sample to the titration vessel.
Replace container on the balance.
Displayed weight transferred to DL35 (negative sign is ignored).
Ensure that the titration stand is tightly sealed, particulary in the trace determination
and during work in an environment with a high atmospheric moisture content.
If possible do not open the titration stand when adding the sample or at least only very
briefly. A few recommendations follow:
Liquid samples

Samples with a water content greater than 10 mg can be

added directly through the opening in the titration head using
a Pasteur pipette (disposable plastic pipette) or syringes. For
the trace determination, the titration station remains closed
with a septum. The sample is injected through the septum
using a syringe. A relatively wide-bore needle is used for
viscous samples.

Solid samples

The accessories include weighing boats made of glass and

plastic that facilitate addition through the opening in the
titration head thanks to the funnel-shaped spout. Depending
on the sample, either a glass or a plastic weighing boat is

more suitable. The important point is that the sample flows

easily out of the boat so that the opening can be closed again
as quickly as possible.
Pastes, greases

Here wide-necked Pasteur pipettes are suitable (disposable

plastic pipettes) or syringes without a needle. Slight warming
facilitates uptake by the pipette.

Normally, several samples can be titrated in succession in the same solvent.

A sluggish end to the titration or a DRIFT that is too high or an excessive subsequent
consumption after the titration can be caused by the following:
Sample dissolves only slowly or poorly: vary solvent, use less sample. Prolong
stirring time. Pulverize sample.
Water is very tightly bound by the sample matrix: vary solvent, titrate at higher
temperature. Predry in the DO301 or DO302 Drying Oven (see applications).
Side reactions also require titrant: titration in cooled solvent, vary solvent or titrant.
Loading limit is reached: change solvent (see section 7.2).

15.

Maintenance

Warning
Never leave unreacted titrant in the titration vessel for a lengthy period as parts made
of silicon such as the septum and tubing connections of the suction tube can be
attacked.
Electrode

With time, certain Karl Fischer reagents and samples have an

adverse effect on the response behavior of the electrode.
The end point recognition is then delayed so that the solution
after the end point is brown and not yellow. Clean the
electrode for a few minutes in an ultrasonic bath with
deionized water or ethanol or place it for 60 seconds in
chromic acid and then rinse it with water or ethanol (dry well
before use).

Molecular sieves

Depending on the moisture content of the ambient air, the

molecular sieves in the drying tubes become ineffective
within 2 to 12 weeks. They can be dried spread out in a
drying oven at 160 - 300 C for at least 24 hours. The
molecular sieves mounted on the waste bottle contain both
water and SO2. Rinse these with distilled water before
regeneration.

Titration stand

Ensure that the inside of the titration head together with the
internal fittings (electrode, burette tip, etc.) is as free from
solvents as possible: When the titration stand is open, wetted
areas adsorb water from the air and this then causes a
relatively large drift owing to slow back diffusion.

Burette

16.

Clean burette cylinder, piston, stopcock and tubing

periodically with ethanol:
Never place the parts in a drying oven at a temperature
higher than 40 C!
Never place O-rings and rubber gaskets in organic solvents!
Lightly grease the piston rod with silicon grease as protection
against corrosion.
Replace the piston if it leaks or its edge is scored.
To achieve a better seal, lightly grease the stopcock with
silicon grease (see section 13.3.4).
Replace the rubber gasket of the stopcock relatively often; it
becomes hard with time.
Remove air bubbles at the piston surface by removing the
burette from the guide and tapping it gently. The air bubbles
rise to the top. Then rinse the burette.
Remove air bubbles in the tubes by tapping them with your
fingers while titrant is being siphoned off or dispensed. If this
does not help, undo the suction tube so that the titrant flows
back into the bottle, screw it on again and rinse the burette.
In obstinate cases, unscrew bothtubes, rinse with deionized
water and ethanol and dry with oil-free compressed air or in
vacuum.

Technical data

Principle
Endpoint indication
Control
Measurement range
Resolution

Result
Accuracy
Reagents
Analysis time
Solvent dispensing/
suction device
Auxiliary functions

Data connections for

Volumetric water determination by the Karl Fischer method.

Voltametric: voltage measurement at a polarized double
platinum pin electrode.
Kinetically controlled by microprocessor.
10 g 500 mg water, a few ppm to 100%.
1/2000 of a burette. This corresponds to 25 g water with a
10 mL burette or 12.5 g water with a 5 mL burette.
(Concentration: 5 mg H2O/mL.)
Automatic reconciliation of the sample weight in the water
content calculation in %, %dm, ppm or mg.
Better than 0.3% with sufficient sample and accurate
weighing and if the water is freely available.
All common pyridine-containing and pyridine-free reagents
can be used.
Typically 12 minutes if the water is freely available.
Addition of solvent and emptying of the titration vessel
By a diaphragm pump.
Determination of the titrant concentration.
Determination of the DRIFT.
Exact dispensing using interchangeable burettes.
Serial by bit current loop data interface for all Mettler-Toldeo

Self monitoring
Magnetic stirrer
Keypad
Plastic parts
Width x depth x height
Weight
Ambient temperature
Power supply
Power consumption
Date/time
Methods
Total titrant
consumption

balances/scales with data output CL and 03 (e.g. AT

balances) and Mettler-Toldeo GA42 alphanumeric printer or
an Epson-compatible dot matrix printer, analog output for line
recorder, Option RS-232-C for a computer.
By microprocessor.
Built in, with variable adjustment.
Splash waterproof.
Polyester (housing), polypropylene (titration stand, other
parts).
25 x 35 x 27 cm
approx. 5.5 kg
10...35 C
100/120 V
230/240 V
(+10%/15%)
50/60 Hz*
600 mA
300 mA
Display and alteration of time and date.
50 freely selectable methods.
Setting of upper limit of total titrant consumption for
several samples.

17.

Accessories

17.1

Standard equipment
Order No.

1 DL35 basic instrument with titration stand incl.

spare fuse
1 Set Operating Instructions
in accordance with your order

see opt. accessories

1 Application Brochure METTLER methods

DL35 Karl Fischer Titrator

724326

1 Memo card in accordance with your order

see opt. accessories

1 Power cable in accordance with your order

see opt. accessories

1 Interchangeable burette 5 mL
incl. burette piston, piston rod,
burette holder, tip holder, dispensing and
suction tube, tube of silicon grease

DV905

1 Drying tube holder

23915

1 Diaphragm pump

23920

1 Solvent dispensing tube

23903

1 Suction tube with tubing

23904

1 Tube and O-ring set

(spare material: wear parts of suction tube)

23946

4 Tubes for air lines

23975

2 Screw caps (1)*

2 Gaskets (1)*

23937
23981

4 Drying tubes with cover (1)*

23961

1 Bottle molecular sieves 250 g

71478

1 Double platinum pin electrode

DM142

1 Magnetic stirring bar

71479

1 Beaker 150 mL

23917

1 Glass stopper

71469

* The order numbers refer to 1 item

1 Septum ST24
Set of 10

23950

1 Phillips screwdriver No. 2

73072

17.2

Optional accessories

1 Set operating instructions

German
English
French

704649
704724
704725

1 Memo card

German
English
French
Spanish
Italian

704743
704744
704745
704749
704750

1 Power cable

Neutral
Germany
USA
Switzerland

87576
87925
88668
87920

1 Beaker 150 mL
1 Beaker 250 mL

23917
23918

1 Fastener ring for 250 mL beaker

23902

1 Flat gasket for titration head

23885

1 Thermostatable beaker incl. fastener ring

23976

1 L Brown glass bottle

71296

1 Flat gasket for 1 L brown glass bottle

23981

Adapter for bottles with different screw threads

(1 in each case):
Thread

Lead [mm]

40.5
37.5
32.5
31
30.5

3.5 (new Merck bottles)

5
3
3.5
3.5

23774
23787
23817
23789
23788

Septum ST10
Set of 10

23949

Septum ST24
Set of 10

23950

Weighing boat, glass,

Weighing boat, glass,
Weighing boat, PE,
Weighing boat, PE,

20 x 60,
30 x 80,
25 x 65,
38 x 100,

set of 5
set of 5
set of 5
set of 5

23951
23952
23953
23954

Syringe 1 mL, pack of 100

Syringe 10 mL, pack of 100

71492
71482

Injection needle
Injection needle

71483
71484

80 x 1.2 mm pack of 12
80 x 0.8 mm pack of 100

1 Three-hole adapter with ST10 and ST7.5 and

needle hole and the appropriate stoppers
1 Set stoppers for three-hole adapter
comprising:

1 ST10 stopper

23982
25883

1 ST7.5 stopper
6 Needle hole stoppers

Microfuses 400 mA*

slow-blow for 230/240 V

Set of 3

51367

Microfuses 800 mA*

slow-blow for 100/120 V

Set of 3

20182

1 Connection cable for Mettler-Toledo AE balances

23778

1 Connection cable for Mettler-Toledo PM, AM, AT balances

23618

1 Data output RS-232-C (DCE)

23955

1 Connection cable for RS-232-C interface, 2 m

male female
male male

59342
59348

1 Interchangeable burette

5 mL
10 mL
20 mL

DV905
DV910
DV920

1 Piston, packed for

DV905
DV910
DV920

1 Piston rod

23636

1 Burette body
incl. stopcock

5 mL
10 mL
20 mL

1 Burette holder

Stopcock parts:
(1 of each)

23710
23711
23712

25724
25708
25725

23645

Valve disk
Rubber gasket
Follower cam
Threaded ring

1 Light protection tube

101003
25737
25715
25716

23644

1 Dispensing tube with siphon tip, 70 cm

25687
Order No.

1 Suction tube, 83 cm

25688

1 Holder for burette tip

23960

1 Tube silicon grease (stopcock grease)

71300

1 Drying oven

120 V
230 V

DO301
DO302

Application Brochures
Water determination following Karl Fischer
Theoretical and practical fundamentals

German
English

724349
724350

Water determination following Karl Fischer in foods,

beverages and cosmetics

German
English

724477
724478

Water determination following Karl Fischer in chemicals,

solvents, mineral oil products and plastics

German
English

724353
724354

METTLER methods DL35 Karl Fischer Titrator

German
English

724325
724326

18.

Malfunctions and their causes

18.1
Instrument malfunctions
The error condition is rectified with [RESET]. Please note error code.
On reoccurrence, the instrument must be serviced by METTLER service.

Err 1

Microprocessor

Err 2

Program storage

Err 3

General data storage

Err 4

Err 5

Configuration data storage. After [RESET] the default values are set
for instrument and method parameters. The 10 original METTLER
methods are also reloaded.
Signal digitalization

Err 6

Burette drive, tip of dispensing tube blocked

Err 7

Stopcock drive, heavy encrustation of stopcock area, stopcock

wrongly mounted
Internal clock blocked. Reinitialize date and time with 91000 [MODE]
then reenter date and time.

Err 8

18.2
Err 10
Err 11

18.3
Err 20
Err 21

Malfunctions in the communication with external devices

Receipt of external data too fast (Option RS-232-C)
Weight transfer from balance. Check configuration of balance setting
(see section 13.4).
Operating errors
Input value too large

Err 22

Result of CONC determination too high:

No sample, wrong standard sample
Maximum volume dispensed (see instrument parameter 5)

Err 23

No weight entry, attached balance not switched on or balance faulty

18.4
EEE

Other error conditions

Nondisplayable numeric value