Metrohm 784KFP User Manual

Mertrohm AG

CH-9101	Herisau/Switzerland
Phone	[phone]
Fax	[phone]
Internet	www.metrohm.ch
E-Mail	[e-mail]

784 KFP Titrino

Instructions for Use

8.784.1003						99.08 / sn

Table of contents
Table of contents
1 Overview...................................................................................................................		2
2 Manual operation .....................................................................................................		6
2.1	Keypad .........................................................................................................................	6
2.2	Principle of data input ..................................................................................................	7
2.3	Text input ......................................................................................................................	8
2.4	Configuration, key <CONFIG>...................................................................................	9
2.5 Key <MODE> ...........................................................................................................		14
2.6 Parameters, key <PARAM> .....................................................................................		15
2.6.1 Parameters for KFT .............................................................................................		15
2.7	Result calculations .....................................................................................................	25
2.8	Statistics calculation...................................................................................................	28
2.9	Common variables .....................................................................................................	30
2.10 Data output...............................................................................................................		31
2.10.1 Reports for the output at the end of a determination .......................................		31
2.10.2 Display of the Curve ..........................................................................................		33
2.11 User name, key <USER> .......................................................................................		34
2.12 Method memory key <USER METH>....................................................................		35
2.13 Current sample data, key <SMPL DATA> .............................................................		37
2.14 Silo memory for sample data...................................................................................		38
2.15 Storing determination results and silo calculations ................................................		41
2.15.1 Storing determination results ............................................................................		41
2.15.2 Silo calculations.................................................................................................		42
2.16 Manual dosing..........................................................................................................		44
3 Operation via RS232 Interface ..............................................................................		45
3.1	General rules ..............................................................................................................	45
3.1.1 Call up of objects.................................................................................................		46
3.1.2 Triggers ................................................................................................................		47
3.1.3 Status messages.................................................................................................		48
3.1.4 Error messages ...................................................................................................		49
3.2 Remote control commands .......................................................................................		52
3.2.1 Overview ..............................................................................................................		52
3.2.2 Description of the remote control commands....................................................		67
3.3	Properties of the RS 232 Interface .............................................................................	90
3.3.1 Handshake ..........................................................................................................		90
3.3.2 Pin Assignment....................................................................................................		93
3.3.3 What can you do if the data transfer does not work?.........................................		95
4 Error messages and Troubleshooting..................................................................		97
4.1	Error and special messages ......................................................................................	97
4.2	Diagnosis..................................................................................................................	100
4.2.1 General ..............................................................................................................		100
4.2.2 Procedure ..........................................................................................................		100
4.2.3 Equipment required:..........................................................................................		101
4.2.4 Diagnosis steps .................................................................................................		101
4.3	Initialize and test RAM..............................................................................................	110
4.4	Releasing a locked spindle......................................................................................	111
		784 KFP Titrino

	Table of contents
5 Preparations .........................................................................................................		112
5.1	Setting up and connecting the instruments ............................................................	112
5.1.1 Titrino with Stirrer or Titration Stand ..................................................................		112
5.1.2 Connection of a printer ......................................................................................		113
5.1.3 Connection of a balance ...................................................................................		114
5.1.4 Connection of a KF Oven ..................................................................................		115
5.1.5 Connection of a Sample Changer ....................................................................		116
5.1.6 Connection of the 774 Oven Sample Processor ..............................................		117
5.1.7 Connection of a computer.................................................................................		118
5.1.8 Connection of a Remote Box ............................................................................		118
5.2	Connection of electrodes and preparing titration vessel ........................................	122
6 Appendix ..............................................................................................................		123
6.1	Technical specifications ...........................................................................................	123
6.2	Pin assignment of the "Remote" socket...................................................................	125
6.2.1 Lines of the "Remote" socket during the titration..............................................		127
6.2.2 Possible configurations of the activate pulse KFT ...........................................		128
6.3	User methods ...........................................................................................................	129
6.3.1 General...............................................................................................................		129
6.3.2 KF Titer determination with H2O or methanol standard "H2OTiter"..................		130
6.3.3 KF Titer determination with sodium tartrate "TarTiter" ......................................		131
6.3.4 Blank determination for KFT "Blank_KF"...........................................................		132
6.3.5 KF-titration with blank value subtraction "KF-Blank".........................................		133
6.3.6 KF-titration without blank value subtraction "KF" ..............................................		135
6.3.7 KF titrations with various KF reagents ..............................................................		137
6.3.8Determination of the bromine number "BrNumber"...........................................		138
6.4	Titrino validation........................................................................................................	139
6.4.1 Electronic tests ..................................................................................................		139
6.4.2 Wet tests ............................................................................................................		139
6.4.3 Maintenance and adjustment of the Titrino ......................................................		139
6.5	Warranty and certificates..........................................................................................	140
6.5.1 Warranty .............................................................................................................		140
6.5.2 Certificate of Conformity and System Validation ..............................................		141
6.6	Scope of delivery and ordering designations..........................................................	143
Index ........................................................................................................................		147

784 KFP Titrino

784 KFP Titrino

Overview

784 KFP Titrino

Instructions for Use

1

Overview

1 Overview

Front view of instrument:

1

2

3

4

5

784 KFP Titrino

2

1

2

3

Overview

Exchange Unit

Display

Control keys and indicator lamps on the Titrino

Key <			>	Power switch

Key < 4 >	Switching stirrer ON/OFF
Key <DOS>	Dosing key. Dispensing is performed as long as
	<DOS> is being pressed. Used e.g. to prepare
	the Exchange Unit. The dispensing rate can be
	set with potentiometer (5).
Key <STOP/FILL>	- Stops procedures, e.g. titrations, conditioning.
	- Filling after manual dosing with <DOS>.
Key <START>	Starts procedures, e.g. titrations, conditioning.
	Identical with key <START> of the separate
Indicator lamps:	keypad.
"COND."	Lamp flashes when conditioning is performed
	and the titration vessel is still wet. It is on if con-
	ditioning is ok.
"STATISTICS"	Lamp is on when the "statistics" function
	(calculation of mean and standard deviation) is
	on.
"SILO"	Lamp is on when silo memory (for sample data)
	is on.

4

5

Setting of display contrast

Controls the dosing rate during manual dosing with <DOS> and subsequent filling

784 KFP Titrino

3

Overview

Rear view of instrument:

Remote

1.784	12
Nr.

A1

E 11

6	RS 232	B

7 A2

10

Pol

8

100 - 240 V

f = 50 - 60 Hz S = 15 W

Keyboard

9 C

Made by Metrohm

Herisau Switzerland

784 KFP Titrino

4

6

7

8

9

10

11

12

Overview

RS232 interfaces

2 separate interfaces for the connection of printer, balance, and computer

Remote lines (input/output)

for the connection of the Remote Box, Sample Changers, robots etc.

Connection of electrodes

∙ 1 measuring input for polarized electrodes, e.g. KF electrode

Connection for separate keypad

Connection for power cable

With power supplies where the voltage is subject to severe HF disturbances, the Titrino should be operated via an additional power filter, e.g. Metrohm 615 model.

Connection for stirrer

728 Magnetic Stirrer, 722 Rod Stirrer, 703 or 727 Ti Stand Supply voltage: 10 VDC (I ≤ 200 mA)

Rating plate

with fabrication, series and instrument number

784 KFP Titrino

5

2.1 Keypad

2 Manual operation

2.1 Keypad

	CONFIG	PARAM	SMPL
			DATA
	STATISTICS	MEAS/HOLD	SILO
	EP	+	–
	7	8	9
	RS	*	/
	4	5	6
	C-FMLA	DEF	USER METH
	C	(	)
	1	2	3
	PRINT	REPORTS	MODE
	MN	ABC	;
	0	.	–
	USER		CURVE
	←	−	→
	CLEAR	↓	ENTER
	STOP	QUIT	START
			6.2130.050

CONFIG Configuration.

PARAM Parameters.

SMPL DATA Sample data.

STATISTICS ON/OFF switching of statistics calculations of consecutive determination, see page 28.

MEAS/HOLD ON/OFF switching of measurements between titrations and hold during titrations.

SILO	ON/OFF switching of silo memory for
	sample data, see page 38.
C-FMLA	Calculation values, see page 27.
DEF	Formulas, data output, see page 25ff.

USER METH Management of internal method memory, see page 35.

PRINT	Printing of reports, see page 33.
REPORTS	Result output.
MODE	Mode dialogue, see page 14.
USER	User name, see page 34.
CURVE	Switching result/curve display, see
	page 33.
←,→	Selection of special values (dialog
	marked with ":").
−,↓	Cursor key for navigation.
CLEAR	Clears values, set special values.
ENTER	Stores values.
STOP	Stops methods.
QUIT	Quits inquiries, waiting times, printing.
START	Starts methods.

The third functions (inscriptions in the triangle) on the keys of the keypad are used for formula entry, see page 25.

784 KFP Titrino

6

2.2 Principle of data input

2.2Principle of data input

∙If you press a key, you will find a group of inquiries in the display.

configuration >monitoring

>peripheral units >auxiliaries

>RS232 settings COM1 >RS232 settings COM2 >common variables

configuration
>peripheral units
	send to COM1:		IBM
	send to COM2:		IBM
	man.reports to COM:		1
	balance:	Sartorius
	stirrer control:		OFF
	remote box:		OFF

Example key <CONFIG>:

In the first line you see where you are: You pressed key <CONFIG> and you are now in the inquiries "configuration".

∙The cursor is inverted. In our example the cursor is on the inquiry ">monitoring". You can move the cursor up and down with keys <−> and <↓>.

∙If a dialog text is marked with ">", it contains a group of inquiries itself. You go to this group pressing <ENTER>.

Example inquiries of "peripheral units":

The first two lines indicate again where you are. Then you find the inquiries.

If a dialog text of an inquiry is marked with ":", you can select a value with keys <←> and <→> (forward/backward).

∙A value is stored with <ENTER> and the cursor moves to the next inquiry.

configuration >monitoring >peripheral units

>auxiliaries

>RS232 settings COM1 >RS232 settings COM2 >common variables

∙With key <QUIT> you move one level up, in our example you go back to ">peripheral units".

If you press <QUIT> once more, you quit the inquiries in "configuration" altogether.

∙If you can scroll, "↓" or "−" appear in the right lower or upper corner of the display.

784 KFP Titrino

7

2.3 Text input

2.3 Text input

			Example storing a method:
	user methods		∙ Press key <USER METH>.
	>store method
			Place the cursor to ">store method" and press
		method name: ********
			<ENTER>.
			The name of the method which is currently in the
			working memory is displayed.

<CLEAR>

REPORTS

ABC

.

user methods >store method:

method name:

ABCDEFGHIJKLMNOPQRSTUVWXYZ abcdefghijklmnopqrstuvwxyz μ°!"#$&'()*+,-./ 0123456789

<QUIT>

user methods
>store method
method name:	Text

<ENTER>

∙Delete this name with <CLEAR>.

∙Open the "text writing mode" with key <ABC>.

You can now select the desired character by means of the cursor keys, then confirm this character. Select the next character...

When you confirmed the last character, i.e. your name is complete, you quit the text writing mode with <QUIT>.

Confirm now the name with <ENTER>.

∙During text input you can correct typing errors with <CLEAR>:

<CLEAR> deletes the characters one by one.

∙If you wish to modify an existing name, do not delete the existing name before you start the text input mode. Proceed then as follows:

1.Press <USER METH>, place the cursor to ">store method" and press <ENTER>.

2.Open the text writing mode directly: Press key <ABC>.

3.<CLEAR> now deletes the characters one by one or you can add additional characters.

4.If your text is complete, leave the text writing mode with <QUIT> and confirm the text with <ENTER>.

784 KFP Titrino

8

2.4 Configuration, key <CONFIG>

2.4 Configuration, key <CONFIG>

						Key <CONFIG> serves to enter device specific data.
		CONFIG				The set values apply to all modes.
						monitoring:
						Monitoring of instrument validation, service interval and
		configuration				printout of diagnostic report.
		>monitoring
						peripheral units:
		>peripheral units
		>auxiliaries				Selection of printer, balance, stirrer control and COM
		>RS232 settings COM1				for manual report output.
		>RS232 settings COM2
						auxiliaries:
		>common variables
						e.g. setting of dialog language, date, time, type of re-
						sult display.
						RS232 settings COM1 and 2:
						RS parameters for the COM's.
						common variables:
						Values of common variables.
						The display texts of the Titrino are shown on the left
						side. The values are the default values.
	>monitoring					Monitoring functions
		validation:	OFF			Monitoring the validation interval (ON, OFF)
						Monitoring is carried out at the end of the titrations and
						when the Titrino is switched on. If the monitoring
						responds the message "validate instrument" appears.
						The message vanishes with <CLEAR>. At the same
						time the counter is reset to zero.
						If "ON" has been set:
		time interval	365 d			Time interval for validation (1...9999 d)
						see also page 139.
		time counter	0 d			Time counter (0...9999 d)
						Counts the number of days since the last time the
						counter was reset.
		service:	OFF			Monitoring the service interval (ON, OFF)
						Monitoring is carried out after the Titrino has been
						switched on. If the monitoring responds the message
						"Service is due" appears. The message vanishes with
						<CLEAR>.
						If "ON" has been set:
		next service	YYYY-MM-DD			Date of next service (YYYY-MM-DD)

784 KFP Titrino

9

2.4 Configuration, key <CONFIG>

		system test report:		OFF	System test report printout (ON, OFF)
					With "ON" the report of the system test is printed out
					after the Titrino has been switched on, see also
					page 139.
		>peripheral units			Settings for peripheral units
		send to COM1:		IBM	Selection of printer (Epson, Seiko, Citizen, HP, IBM) at
					the Titrino COM1
		send to COM2:		IBM	"Epson", for Epson
					"Seiko", e.g. for DPU-414
					"Citizen", e.g. for iDP 562 RS
					"HP" e.g. for Desk Jet types. Place curves always at the
					beginning of a page as you cannot have them over 2
					pages.
					"IBM" for all printers with IBM character set Table 437
					and IBM graphics, as well as for the data transmission
					to a computer or a data system.
		man.reports to COM:		1	COM of Titrino for the output of manually triggered
					reports (1, 2, 1&2)
					Manually triggered reports (e.g. with <PRINT> ....).
					Exception <PRINT><REPORTS>: These reports are
					outputted on the COM as defined in the method.
		balance:	Sartorius		Selection of balance (Sartorius, Mettler, Mettler AT,
					AND, Precisa)
					Sartorius:	Models MP8, MC1
					Mettler:	Models AM, PM and balances with 011,
						012, and 016 interfaces
					Mettler AT:	Model AT
					AND:	Models ER-60, 120, 180, 182, FR-200, 300
						and FX-200, 300, 320
					Precisa:	Models with RS232C interface
		stirrer control:		OFF	Automatic switching ON/OFF of the stirrer in the titration
					sequence (ON, OFF)
					If stirrer control is ON, the stirrer will be switched on at
					the beginning and switched OFF at the end of a de-
					termination. For KFT with conditioning the stirrer will be
					switched off in the inactive state.
					For stirrer control the red switch on the stirrer unit must
					be ON.
		remote box:		OFF	Connection of a remote box (ON ,OFF)
					To the remote socket for PC keyboard and barcode
					reader, see page 118.
					If "ON" has been set:
		keyboard:		US	Type of PC keyboard (US, German, French, Spanish,
					Swiss.)
					The PC keyboard is used as an input aid, see
					page 119.
						784 KFP Titrino
10

							2.4 Configuration, key <CONFIG>
		barcode:		input		Target for barcode reader (input, method, id1, id2, id3,
						smpl size)
						The barcode reader is used as an input aid, see
						page 118.
						Input:	The barcode string goes to the entry field in
							which the cursor is currently located.
						Method:	The barcode string goes to the entry field
							"Methods" in the silo memory.
						Id1:	The barcode string goes to the entry field
							"Id1". (Similar for Id2 and Id3.)
						Smpl size: The barcode string goes to the entry
							field "smpl size".
		>auxiliaries				General settings
		dialog:		english		Selection of dialog language (english, deutsch,
						français, español, italiano, portugese, svenska)
		date	1999-08-15			Current date (YYYY-MM-DD)
						Format: Year-month-day, entry with leading zeros.
		time		08:13		Current time (hh-mm)
						Format: Hours-minutes, entry with leading zeros.
		run number		0		Current run number for result output (0...9999)
						The sample number is set to 0 when the instrument is
						switched on and incremented on every determination.
		auto start		OFF		Automatic start of titrations. (1...9999, OFF)
						Number of automatic starts ("number of samples").
						Used for instrument interconnections in which the
						external instrument does not initiate a start. Not
						advisable in connections with Sample Changers.
		start delay		0 s		Start delay (0...999999 s)
						Delay time after start of methods. Abort start delay time
						with <QUIT>.
		result display:		bold		Type of result display at the end of the determination
						(bold, standard)
						bold: The calculated results are displayed in bold
						characters.
						standard: Displays the whole information, e.g. results,
						endpoints, messages etc.
		dev.label.				Individual identification of devices (up to 8 ASCII
						characters)
						Will be printed in the result report, see page 32.
		program		784.0010		Display of program version

784 KFP Titrino

11

2.4 Configuration, key <CONFIG>

>RS232 settings COM1		Settings of RS232 interface
		see also page 90 Identical for COM2.
baud rate:	9600	Baud rate (300, 600, 1200, 2400, 4800, 9600, 19200,
		38400, 57600, 115200)
data bit:	8	Data bit (7, 8)
stop bit:	1	Stop bit (1, 2)
parity:	none	Parity (even, odd, none)
handshake:	HWs	Handshake (HWs, SWline, SWchar, none)
		see page 90.
>common variables		Values of the common variables
C30	0.0	Common variables C30...C39 (0.. ± 999999)
etc.		The values of all common variables are displayed. For
		creating common variables see page 30.

Settings with key <CONFIG> and power ON

Proceed as follows:

1.Switch the Titrino OFF.

2.Press <CONFIG> and keep it pressed during switching the Titrino ON. The display shows the following:

Setup		lock:
	>lock
		Locking keys <CONFIG>, <PARAM> and <SMPL
	>curve
		DATA>, and the functions "recall method", "store
		method" and "delete method" of the internal method
		memory in the Titrino.

			curve:
			Changes the appearance of the curve printout.
	>lock		lock
			"ON" means that the corresponding function is not
			accessible anymore.
	<configuration>:	OFF	The corresponding key is locked.
	<parameters>:	OFF
	<smpl data>:	OFF
	recall method:	OFF	The corresponding function in the internal method
	store method:	OFF	memory of the Titrino is locked.
	delete method:	OFF

784 KFP Titrino

12

2.4 Configuration, key <CONFIG>

>curve

grid:	ON
frame:	ON
scaling:	Full

width

0.5

length

0.05

curve

The settings are valid for COM1 and COM2.

If you change the printer type, the following settings are initialized according to the printer.

Grid drawing (ON, OFF)

Frame drawing (ON, OFF)

Type of scaling (Full, Auto)

Full: The scaling goes from the greatest to the smallest value.

auto: The scaling from tick to tick, e.g. the smallest/greatest values lie in between the first/last tick.

Width (0.2...1.00)

1 is greatest width. If you set 1, you may loose the label at the right margin.

Length (0.01...1.00)

Time axis:

Curve length

0.01100 cm

0.110 cm

0.52 cm

1

1 cm

784 KFP Titrino

13

2.5 Key <MODE>

2.5 Key <MODE>

MODE

;

–

mode

mode: KFT measured quantity: Ipol

With the key <MODE> the dialogue „mode“ is opened.

The 784 Titrino is a titrator, specially designed for Karl Fischer water determinations. It has exclusively the mode KFT (Karl Fischer Titration).

With <ENTER> the selection of the measured quantity is activated. Select Ipol or Upol with <←> or <→> and confirm it also with <enter>.

The following modes can be selected:

∙KFT: Karl Fischer Titration, the determination of water content.

The mode KFT is equipped with a set of standard parameters. They only need few settings in order to be ready to work.

784 KFP Titrino

14

2.6 Parameters, key <PARAM>

2.6 Parameters, key <PARAM>

	The key <PARAM> is used for the entry of values that
PARAM	determine the modes. Values marked with "cond." are
	accessible during the conditioning in the KFT mode.
	"**titr." means that these values can be changed dur-
	ing the titration. They influence the ongoing determina-
	tion. Other values can only be changed in the inactive
	state.
	The display texts of the Titrino are shown on the left
	side. The values are the default values.

2.6.1 Parameters for KFT

					control parameters:
	parameters
		>control parameters			for the EP.
		>titration parameters
					titration parameters
		>stop conditions
		>statistics			control the general course of the titration.
		>preselections			stop conditions:
					Parameters for the termination of the titration.
					statistics:
					Calculation of mean values and standard deviation,
					see page 28.
					preselections:
					ON/OFF of various auxiliary functions such as auto-
					matic requests after the start and activate pulse.
	>control parameters				Control parameters
		EP at U	250 mV		Endpoint (input range depending on the measured
		cond.			quantity:
					U, Ipol: 0.. ±2000 mV
					I, Upol:	0...±200.0 μA)
		dynamics	100 mV		Control (input range depends on the measured
		**titr.			quantity:
					U, Ipol: 1...2000 mV
					I, Upol:	0.1...200.0 μA)
					Outside of the control range: constant dosing, see
					page 21.

784 KFP Titrino

15

2.6 Parameters, key <PARAM>

		max.rate	max. ml/min		Maximum dosing rate (0.01...150 mL/min, max.)
		**titr.			<CLEAR> sets "max.".
					This parameter determines primarily the addition rate
					outside the control range, see page 21.
					The maximum rate depends on the Exchange Unit:
					Exchange Unit		max. rate
						5 mL	15 mL/min
					10 mL		30 mL/min
					20 mL		60 mL/min
					50 mL		150 mL/min
		min.volume incr. min. μl			Minimum volume increment (0.1...9.9 μL, min.)
		**titr.			<CLEAR> sets "min.".
					This parameter determines the addition rate at the start
					and the end of the titration, see also page 21.
					This parameter influences the titration speed and
					therefore its accuracy very strongly: A smaller
					"min.volume incr." results in a slower titration.
		stop crit:		drift	Type of stop criteria (drift, time)
		**titr.			Titration stops, if EP and stop drift are reached
		stop drift		20 μl/min
		**titr.			(1...999 μL/min)
		t(delay)		10 s	Titration stops if there is no dosing during t(delay)
		**titr.			(0...999 s, INF)
					<CLEAR> sets "INF".
					Switch off when EP is reached and the set time after
					the last dosing has elapsed.
					If t(delay) is "INF"
		stop time		OFF s	Stop after a time (0...999999 s, OFF)
		**titr.			<CLEAR> sets "OFF".
					Stop after the set time after start of titration. "OFF"
					means no stop, i.e. titration for an "infinitely" long time.
		>titration parameters			Titration parameters
		titr.direction:		–	Direction is set automatically (+, –, auto)
					auto:	The direction is set automatically by the Titrino.
					+:	Direction of higher voltage (more "positive"),
						larger currents.
					– :	Direction of lower voltage, smaller currents.
		pause 1		0 s	Pause 1 (0...999999 s)
		**titr.			Waiting time before start volume, e.g. for equilibration
					of the electrode after start. The waiting time can be
					aborted with <QUIT>.

784 KFP Titrino

16

2.6 Parameters, key <PARAM>

start V:	OFF
cond.
start V	0.0 ml
cond.
factor	0
cond.
dos.rate	max. ml/min
**titr.
pause 2	0 s
**titr.
extr.time	0 s
**titr.
I(pol)	50 μA
U(pol)	400 mV
electrode test:	OFF
temperature	25.0 °C
cond.
time interval	2 s
cond.

Type of start volume (OFF, abs., rel.)

"OFF": start volume switched off "abs.": absolute start volume in mL

"rel.": relative start volume to sample size.

If "abs." is set:

Absolute start volume (0...999.99 mL)

If "rel." is set:

Factor for relative start volume (0...±999999).

Calculated as: start V in mL = factor sample size

Dosing rate for start volume (0.01...150 mL/min, max.)

<CLEAR> sets "max.".

The maximum rate depends on the Exchange Unit:

Exchange Unit	max. rate
5 mL	15 mL/min
10 mL	30 mL/min
20 mL	60 mL/min
50 mL	150 mL/min

Pause 2 (0...999999 s)

Waiting time after start volume, e.g. reaction time after dosing of a start volume. The waiting time can be aborted with <QUIT>.

Extraction time (0...999999 s)

During this time the titration is running. It will not be stopped (also if EP is already reached), before the extraction time is terminated. The extraction time can be aborted with <QUIT>.

Polarization current (–127...127 μA) or the

polarization potential (–1270...1270 mV, in steps of 10 mV) is inquired.

Electrode test (OFF, ON)

Test for polarized electrodes. Performed on changeover from the inactive standby state to a measurement. "OFF" means that the test is not performed.

Titration temperature (–170.0...500.0 °C).

The temperature can be entered manually.

Time interval (1...999999 s)

Time interval for acquisition of a measured value into the measuring point list.

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17

2.6 Parameters, key <PARAM>

		>stop conditions		Stop conditions for titration
				If this is not "normal", i.e. after reaching the EP
		stop V:	abs.	Type of stop volume (abs., rel., OFF)
		**titr.		"abs.":	absolute stop volume in mL
				"rel.":	relative stop volume to sample size
				"OFF": stop volume switched off. Stop volume is not
					monitored.
				The stop volume applies for one single titration. The
				conditioning volume is not monitored.
		stop V	99.99 ml	If "abs." is set:
		**titr.		Absolute stop volume (0...9999.99 mL)
		factor	999999	If "rel." is set:
		**titr.		Factor for relative stop volume (0...±999999)
				Calculated as: Stop V in mL = factor sample size
		filling rate max. ml/min		Filling rate after titration (0.01...150 mL/min, max.)
		**titr.		<CLEAR> sets "max.".
				The maximum rate depends on the Exchange Unit:
				Exchange Unit		max. rate
				5 mL		15 mL/min
				10 mL		30 mL/min
				20 mL		60 mL/min
				50 mL		150 mL/min
		>preselections		Preselections for the sequence
		conditioning:	ON	Automatic conditioning of titration vessel (ON, OFF)
				If conditioning is "ON", the solution is constantly kept at
				the endpoint.
				When conditioning is performed, the volume drift can
				be displayed during the conditioning:
		display drift:	ON	Display of drift during conditioning (ON, OFF).
		cond.		Volume drift.
		drift corr:	OFF	Type of drift correction (auto, man., OFF)
		cond.		Type of drift correction: (EP – drift time)
				auto: drift value at start is valid
				man.: see below
				OFF : no correction
		drift value	0.0 μl/min	Value for manual drift correction (0.0...99.9 μL/min)
		cond.
		req.ident:	OFF	Request of identifications after start of titration (id1,
		cond.		id1&2, all, OFF)
				After start, sample identifications can be requested
				automatically: Only id1, id1 & id2, all three id's or no
				inquiries.
						784 KFP Titrino
18

2.6 Parameters, key <PARAM>

req.smpl size:

OFF

cond.

limit smpl size: OFF cond.

low lim.	0.0
cond.
up lim.	999999
cond.
oven:	no
cond.

activate pulse: OFF cond.

Request of sample size after start of titration (value, unit, all, OFF)

"all" the value and the unit will be requested.

Limiting value check for sample size (ON, OFF)

With "ON" the error message "sample size out." appears if the entry is outside the set limits. The limiting values are shown in the display window.

The absolute value of the limit is checked during sample size input and during the calculation of the results.

If "ON" has been set:

Lower limit for sample size (0.0...999 999)

Upper limit for sample size (0.0...999 999)

Connected oven (COM1, COM2, no)

COM of the Titrino to which the oven is connected. If an oven is connected via RS232 an inquiry will be made for the oven results and these will be inserted

into the result report of the Titrino. The report output on the oven must be switched OFF (see also page 115). Set "no" if no oven has been connected or if you have not connected the oven to Titrino the via RS232 interface.

Pulse output on I/O line L6 (L6, pin 1) of the remote socket (first, all, cond., OFF) e.g. start of a Dosimat, see page 126.

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19

2.6 Parameters, key <PARAM>

Titration sequence of KFT

<START>

(Activate pulse) (Stirrer ON)

(Start delay)

(Preconditioning)

(<START> (Activate pulse) (Start delay)

(Request ident.) (Request smpl size)

(Start conditions)

(Extraction time) Titration with test of stop criterion

(Stirrer OFF)

Calculations

Data output

After the start, the activate pulse is outputted and the stirrer switched on.

The start delay time is waited off.

If conditioning is on, the sample solution is titrated until the EP is reached. The display shows then

drift OK

2.3 μl/min

or

KFT conditioning

The vessel is now conditioned. The titration can be started with <START>.

The sample identifications and the sample size are requested.

Pause 1 is waited off, the start volume is dispensed and pause 2 waited off.

The titration is executed. If the extraction time is not yet over when the endpoint has been reached, the titration will only be terminated after the extraction time is over.

The stirrer is switched off when there is no conditioning.

Calculations are carried out.

Data are outputted.

(Reconditioning)

Conditioning is carried out.

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20

2.6 Parameters, key <PARAM>

Control parameters for KFT

The control parameters can be set according to your samples. The default parameters are already set to get satisfactory results. Optimize the control parameters for specific samples only.

During the titration, reagent dosing is carried out in 3 phases:

U/mV

KFT Ipol

EP

V/mL

t/s

					V/mL
Initial		Continuous
				Control
dosing		dosing		range

1.Initial dosing:

Here the dosing rate increases constantly up to "max.rate".

2.Continuous dosing: Dosing is performed at the maximum rate "max.rate" until the control range (dynamics) is reached.

3.Control range (dynamics): In this range, dosing is performed in single steps. The last dosing steps are controlled by the parameter "min.volume incr.".

I/uA

EP

KFT Upol

V/mL

Remarks:

∙Titer determination should have the same modes and the same parameters as the sample titrations.

∙In most cases the preset default parameters provide precise and reproducible results.

∙Ipol gives relatively steep curves. They are flatter with Upol.

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21

2.6 Parameters, key <PARAM>

Mechanisms of the KFT parameters in Ipol mode

U/mV
+	Titration		Excess H2O
	(direct titration)
		EP at U
			Excess Iodine-

Titration (Back titration) darker

solution

I(pol)

+

I/μA

∙The position and curve characteristics of the line between the ranges of excess water or excess iodine depends on the type of sample and the ingredients of the working media.

∙The endpoint has to be set close to the range margin, but always within the iodine excess range. If the endpoint is set too close to the limit, an overdose of KF reagent may be dispensed. The steeper the curve at the preset polarization current I(pol), the more delicate it is to titrate to a steady and reproducible endpoint. For the titration of troublesome samples, the particular conditions must be optimized by trial and error. Always mind the color of the working medium at the end point as your guideline. Remark: In most cases the preset default parameters provide precise and reproducible results.

∙If you select negative values for a parameter, you should choose negative values for all other parameters too in order to have compatible parameter sets.

∙In KFT Upol mode, all parameters work in a similar manner as in KFT Ipol mode.

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2.6 Parameters, key <PARAM>

The determination of the free water is easily done, as far as the specifications of the reagent manufacturer regarding the "water capacity" of the reagents are considered. Problems may occur with specific sample matrices. The relevant literature contains many precise analysis instructions. Here, we give you some useful hints for the sample addition.

Sample addition

For sample addition various accessories are available, for example injection syringes, weighing spoons etc.

It is a good idea to apply the back-weighing technique, except when you are disposing small amounts of liquids with a micro-syringe. Fill the syringe or the weighing spoon with your sample just before the titration (e.g. during conditioning) and tare it on a balance with an appropriate precision, which ideally is connected to the Titrino. Sample size request should always be switched on (see page 19). Add the sample during the request for the sample size, and weigh the syringe or weighing spoon again to evaluate the weight difference. Use the transfer of balance data to enter the correct sample size if possible. The weight has to be transmitted in gram. If you transfer the sample size from the balance, the sample size request is confirmed automatically, and the titration is started at once. Otherwise use the keypad to enter the weight.

If the sample size request is switched off, and preconditioning is set, you are explicitly prompted to add your sample. For six seconds, the message "add sample" is displayed after which the titration is started by the Titrino itself. This waiting time can be extended by pressing <MEAS/HOLD>.

Solid samples

Use the glass weighing spoon 6.2412.000 and dispose the sample through the opening for the septum stopper.

Liquid samples

Use a disposable syringe (2...20 mL) or a micro-syringe with a long needle attached. Puncture the septum and dispose the sample carefully. When using disposable syringes, add the liquid sample carefully without dipping into the solvent. Draw back the last drop of sample into the syringe before you redraw the needle. For disposing an exact, small volume of liquid sample, use a micro-syringe. Proceed as described above, but dip the needle into the preconditioned solvent and dispose the sample carefully. Here drawing back of solvent or sample adhering to the needle is not recommended.

Always keep in mind to exchange the septum as soon as it shows any large punctures impairing the tightness of the titration cell.

Pasty, viscous samples

For samples which cannot be disposed with a needle because of their high viscosity, you can handle your samples with disposable syringes with a large volume without using a needle. Dispose your sample through the opening of the septum stopper. Back-weigh the syringe after addition of the sample. Be sure to wipe off any adhering excess sample substance of the syringe before taring it.

In any case, pay attention to prevent the penetration of atmospheric moisture into the titration vessel when you are disposing the sample. If you still have to open the titration cell for any reason, determine a blank value and take it into account for the calculation of the titration result (see page 132).

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23

2.6 Parameters, key <PARAM>

In the following table we attempt to show you solutions related more to the instrument's side:

What to do if ...

Problem	Possible causes and remedial action
Dosing at end too long and	∙	Increase "min.volume incr.".
increments too small. "Is never	∙ Change stop criterion. Try to increase stop drift or
finished!"		use a short stopping time as stop criterion, e.g.
	∙ For problematic samples change solvents with
		ketones or aldehydes in 2-methoxyethanol or with
		amines mixture in methanol/glacial acetic, e.g., see
		literature.
The increments at the end of the	∙ Lower "max.rate". The following experiment gives you
titration are too large.		a reference point for the optimum max.rate: Drift
"Overshoots".		display during conditioning and add sample without
		starting the titration. Select a value below the
		maximum drift as "max.rate".
	∙ Optimize setup of electrode and buret tip and
		improve stirring.
Solution becomes too brown at	∙ The methanol fraction in the solvent is too low.
the end of the titration.		Change the solvent.
	∙ Electrode could be coated; wipe off with acetone.
Solution becomes darker with	∙	Renew solvent.
every titration.	∙ Electrode could be coated; wipe off with acetone.
The drift increases with every	∙ Does your sample evolve water extremely sluggishly?
titration.		Work with the KF oven.
	∙ Are acids esterified in your sample? Change solution
		more frequently. Increase buffer capacity of the
		solvent.
	∙ Does your sample contain ketones or aldehydes?
		Use special reagents suitable for ketones and
		aldehydes.
The endpoint is reached "too	∙	Reduce "max.rate".
rapidly".
The titration times become	∙ With 2-component reagents the buffer capacity of the
longer and longer.		solvent can be exhausted. Change solution.
	∙ If the drift increases at the same time, see above.

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2.7 Result calculations

2.7 Result calculations

Formula entry, key <DEF>

		DEF		Key <DEF> contains various inquiries for result
(				calculations and data output. The data of this key are
2
				method specific and they are stored in the method
				memory together with the method.
	def			formula:
		>formula
		>silo calculations		Formulas for result calculations.
		>common variables
		>report
		>mean		The display texts of the Titrino are shown on the left
				side. The values are the default values.
	>formula			Input of formulas
		RS?		Enter formula number (1...9)
				You can calculate up to 9 results per method.
				Enter a number 1...9.
		RS1=		Input of formula
				Example:
		RS1=EP1 C01/C00		RS1=EP1 C01/C00
				Enter formula by means of 3rd functions of keyboard.
				Here you will find operands, mathematical operations
				and parentheses. Operands require a number as an
				identification. You can use the following operands:
				EPX: EP's. X = 1...9
				RSX: Results which have already been calculated with
				previous formulas. X = 1...9
				CXX: Calculation constants. XX = 00...45
				Rules:
				∙ Calculation operations are performed in the
				algebraic hierarchy: and / before + and –.
				∙ Store formula with <ENTER>.
				∙ Calculation quantities and operands can be deleted
				with <CLEAR> one by one.
				∙ To delete a complete formula press <CLEAR>
				repeatedly until only RSX remains in the display.
				Confirm with <ENTER>.
				If a formula is stored with <ENTER>, result text,
				number of decimals, result unit and the settings of the
				result limit control will be requested:

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25

2.7 Result calculations

RS1 text	RS1
RS1 decimal places	2
RS1 unit:	%
RS1 limit control:	OFF
RS1 low lim.	0.0
RS1 up lim.	0.0
RS1 L13 output:	OFF

Text for result output (up to 8 characters)

Text input see page 8.

Number of decimal places for result (0...5)

Selection of result unit (%, ppm, g/L, mg/mL, mol/L, mmol/L, g, mg, mL, mg/pc, s, mL/min, no unit or up to 6 characters).

Limit control for the result (ON, OFF)

The limits are checked each time a result is calculated.

If "ON" has been set:

Lower limit (0.0...999 999)

Upper limit (0.0...999 999)

Sets line L13 of the remote socket (OFF, active, pulse) if the result lies outside the limits.

Enter next formula, e.g. for RS2.

Meaning of the calculation variables CXX:

C00	Sample size, see page 37.
C01...C19	Method specific operands, see page 27. They are stored with the
	method in the method memory.
C21...C23	Sample specific operands, see page 37ff.
C26, 27	Mean values from silo calculations, see page 41ff.
C30...C39	Common variables.
C40	Initial measured value of the sample.
C41	End volume.
C42	Determination time.
C43	Volume drift for KFT with conditioning.
C44	Temperature.
C45	Dispensed start volume.

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26

2.7 Result calculations

Input of method specific operands C01...C19, key <C-FMLA>

C-FMLA

C

1

With <C-FMLA> the operands C01...C19 can be put in. For the calculation, the operands are used, which were introduced in the formula.

The inputs method specific and are store in method memory.

The calculation report can be printed with the key sequence

<PRINT><←/→> (press keys repeatedly until "calc" appears in the display) <ENTER>.

Example for a calculation report:

'fm				Calculation report
784 KFP Titrino	02134	784.0010
user	sn
date 1999-08-15	time 15:01		3
KFT Ipol	KF-Blank			mode und method name
>calculations				formulas:
Water=(EP1-C38)*C39*C01/C00/C02;2;%				result name=formula;number of decimal
Titer=C39;4;mg/ml				places;result unit
Blank=C38;4;ml
C00=	1.0			sample size
C01=	0.1			method specific operands
C02=	1
C38=	0.0			values of the common variables that are
C39=	0.0			used
------------

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27