Operating Instructions METTLER TOLEDO DL21 Titrator DL25 TitratorTable of contents: eetonrene? Peep a4 32 44 42 51 52 53 61 62 7A 72 Preliminaries Indroduction| Installation procedure ‘Switching on the instrument Entering the date General information Switching on the stirrer in the standby mode Displaying the measuring signal Blocking and unblocking critical key functions Maintenance Titrant preparation and dispensing Titrant concentration CONC How to use the interchangeable burettes Filling the burette Dispensing Titration How to perform a titration Printing out additional information Titration methods How to select, display, change and store methods Printing out methods and list of methods Adapting the parameters to the titration Configuration ‘System configuration (configuration parameter 8) Configuration parameters 1 through 7 Result calculation Entering and checking the calculation constant CONST Special calculations The titrant concentration CONC Entering CONST REAG Performing a CONC determination Calibration of the pH electrode Performing a calibration ‘Manual entry and checking of the electrode parameters Dispensing and measurement as a method Dispensing Measurement ©emear roe METTLER DL21/DL2510. 10.41 1. 12. 12.1 12.2 13. 13.1 132 133 13.4 14, 144 142 15. 15.1 162 16. 16.1 7. 174 172 173 174 175 176 177 18. End point titration ‘Two end points. p- and m-values, Acid and base number TAN/TBN Titration according to ASTM D664/D4739 Equilibrium titration according to ASTM 02896 pH-stating Data storage and printout Time window Entering the time window How to perform a pH stat titration ‘Special evaluation procedures Determination of the minimumy/maximum of a titration curve Titration curves with linear sections (segmented curves) Back titration How to determine the excess How to perform a back titration Blank How to determine the blank Series titration ‘Sample entry How to perform a series titration Statistical evaluation Checking and alteration of series sample data Series titration without sample entry Rinsing, dosing, titration and conditioning with the ‘ST20A/ST20 Sample Changer ‘Manual operation of the ST20A/ST20 Sample Changer Remote contro! a 45 46 aT 49 49 49 50 53 64 55 56 56 METTLER DL21/DL25‘Appendix A: Appendix B: ‘Appendix C: ‘Appendix D: ‘Appendix E: Appendix F: ‘Appendix G: ‘Appendix H: Appendix I: Technical specifications Standard equipment and optional accessories Standard equipment Optional accessories Installation procedure Checking the operating voltage Changing the operating voltage Setting up the titration system Installation and maintenance of the interchangeable burettes. Peripherial instruments ‘Switching on Errors and malfunctions Error messages Faults, possible causes, remedial action Glossary (Technical General terms Units rms) Description of the technical data for instruments conforming to IEC-348 Applications and standard method 0 Index Configuration data 15 78 78 79 86 86 86 87 Ey 93 94 95 100 100 102 103 105 106 108 METTLER DL21/DL25Preliminaries 1.1 Introduction The DL25 and D121 Titrators are complete analysis stations fortitimetric. analyses. They enable a titration to be performed and evaluated automatically. Consideration of the sample weightin the result calculation allows the analysis to be reported in the desired unit. A particular feature of the DL25/21 Titrators is their simple, easy-to- understand operation. The setup procedure for a particular analysis avoids the use of technical instrument parameters, which would be unfamiliar toa chemist. In very many cases, atitration can be carried out with optimum accuracy using just the standard configuration. Before the start ofa titration, a request is made for sample weight and ‘sample identification number. The rest of the procedure is automatic. A balance and a printer forthe result record can be directly connected and, no additional equipment is required. Special auxiliary functions support the determination of the titrant concentration (titer determination) as well as determination of the blank value required for certain analyses. The DL25 Titrator allows storage of 50 complete methods. It is thus especially suitable for use in situations where a workstation has tobe set upforseveral analyses. Theless expensive DL21 Titrator with no method storage is particularly well suited to dedicated (single-method) workstations. When the Mettler-Toledo ST20A/ST20 Sample Changer is connected, the DL26/DL21 Titrator becomes a titration station for the automatic analyses ofa series of samples. Upto 20 samples in the standard beaker (100mL) orupto 14 samplesin the larger beaker (250mL) canbe titrated. In addition to rinsing of the titration head inserts after every titration, the ‘ST20A Sample Changer alsoallows versatile sample preparation: dilution, dosing of an auxiliary solution and adjustment ofa pH value. Beakers with wash or conditioning solution can be inserted between samples; this is especially important in the acid and base number determination of petroleum products. ‘The DL25 Titrator allows remote control of a second DL25, anda special feature ofthe instrumentis the extremely simple connection toa computer (LIMS, robot, ...) With the exception of a few points in Section 4, these Operating Instruc- tions apply to both the DL25 and DL21 Titrator. METTLER DL21/DL251.2 Installation procedure To install the instrument, please refer to the instructions given in ‘Appendix C. 1.3. Switching on the instrument As a test, all display elements light up briefly when the instrument is switched on. 1.4 Entering the date ‘This can be effected directly after the instrument has been switched on: ‘The date can be entered directly after the instrument has been switched on: Entry of day, month and year (3 values) for printout of the date with the result record: Key in three sets of numbers and confirm each set with [RUN]. [RESET], if the entered values do not have to be changed. Allthe indicator lamps of the display column rom“ WEIGHT 'to"BUFFER 8” are off Entry when on standby without switching the instrument off. The year can. bbe entered and printed out as a 2- or 4-digit number, but appears only as a 2-digit number in the display. METTLER DL21/DL25 71.5 General information Abort All operations can be aborted by pressing this key. The burette is filled, it necessary. Any error message must be cancelled by pressing [RESET] to continue working. The displays setto zero, orthe last results displayed again ifthe tation data are stil in storage. Clear entry Press this key to clear incorrectly entered numbers. Entering a numeric value (CONC, CONST REAG, BLANK, BACK, CONST, METHOD) ‘Type in the value and press the corresponding parameter key, e.g. [CONC], Checking the stored value of a parameter (CONC, CONST REAG, BLANK, BACK, CONST, METHOD). By pressing the corresponding parameter key, the stored value is displayed until the key is released. 1.6 Switching on the stirrer in the standby mode This function is used to recheck and adjust the stirring intensity with a control knob at the right side of the housing. Stirreris switched on. 1.7. Displaying the measuring signal Measurement and display of the potential in mV. Measurement and display of the potential in pH units. ‘The stirrer is switched on automatically METTLER DL21/DL25‘MODE| MODE| ApH electrode must be attached to the DL25/DL21 for this and calibrated in the manner described on page 35 (measurement as a method, see Section 9.2). Abort by [RESET]. ‘The measuring signal s transferred at rate of 5 values per second to the RS232C interface concurrent with the signal display in mV or pH. 1.8 Blocking and unblocking critical key functions Ifthe titrations tobe performed are always the same, the instrument can be protected against any accidental change in the methods. Blocking The following functions are blocked: Writing over of CONC, CONST, CONST REAG, BLANK, BACK Determination of CONC, BLANK and BACK Changing the configuration data pH calibration and writing over of electrode parameters ‘Changing the sample data of the series. Unblocking ‘The above functions can now be used again. 1.9 Maintenance Electrodes ‘The combined glass electrodes should be cleaned occasionally first in ‘moderately concentrated acid and then, after thorough rinsing, in an ultrasonic bath. See also the Maintenance Instructions packed with the electrode. Burettes Periodic cleaning of the burette cylinder, piston and stopcock and tubing with ethanol is recommended. To clean the tubes, simply run acleaning solution through them. For more details, see page 92 ‘The assembly of the burette parts is described on page 90. METTLER DL21/DL25 9‘Standby CONC Titrant preparation and dispensing 2.1 Titrant concentration CONC ‘The titrant concentration (see also definition in the Glossary, page 100) is stored in the DL26 Titrator as the CONC parameter in mole per liter (equivalent to mmolimL). For very accurate titrations, it should be determined periodically using a calibration sample (standard solution, primary standard), see Section 7. If very stable titrants are used, a single determination or a manual entry is sufficient. The titrant, its concentration and the date are inscribed on the label plate of the burette. Manual entry of the CONC value Enter the titrant concentration (in mol/L) and press the [CONC] key. To enter the known titrant concentration, the value normally specified in ‘molesiliter multiplied by the titer should be keyed in. Example: Equivalent concentration 0.1 mol/L -» CONC = 0.1 + 0.98 = 0.098 mol. Titer: 0.98 Checking the stored CONC value The stored value is displayed as long as the [CONC] key is pressed. 10 METTLER DL21/DL252.2 How to use the interchangeable burettes Slide the required interchangeable burette on the holder rackofthe DL25/ DL21 and, with the knurled sorew turned tothe right, position itabove the drive. When itis evident that the burette has snapped in, turn knurled screw to the left and tighten slightly in order to take up the slack between the holder rack and the burette. For the maintenance of the burette, see page 92. After every reagent change, the titrant concentration specified on the label plate of the burette must be inputted as CONC value (DL21) or the ‘method changed to one with the correct CONC value (DL25). 2.3 Filling the burette ‘The burette is filled by pressing the [BURET/mL] key. To eliminate air ‘bubbles from the burette, carry out a least three burette strokes (10 mL. burette). For filing the burette and, in particular, for removal of air bubbles, the function [BURET/mL] mustbe used without input of a quantity. (This isthe only way in which the burette can be zeroed with the stopcock positioned for delivery.) If after several burette strokes there are still some air bubbles in the system, they can be eliminated by alternately pressing the [BURET/mL] and [RESET] keys and by gently tapping the tubes. If an ultrasonic bath is available, degassing of the solution before use is recommended. It is often not possible to eliminate small air bubbles directly. The procedure outlined below is based on the fact that small bubbles are absorbed by larger bubbles: METTLER DL21/DL25 "Standby BURET| Unscrew suction tube of burette and wait until titrant has completely flowed back into the bottle. Reconnect tube to the burette. Rinse burette once as described above (press [BURET/mL] key). The content ofthe buretteis dispensed andthe burette efiled. This procedure Sucks ai Out of the tube. Slide burette out of the burette holder and place it upside down. Shake itgently untilall existing small airbubbleshave been completely absorbed by the large bubble. Again install burette. ‘Again rinse burette 1 or2times (press [BURET/mL] and [RESET] keys). 2.4 Dispensing A reagent can be dispensed rapidly and accurately with the help of the [BURET/mL] function. The burette volume is defined with parameter 4 (see page 28). Key in the volume to be dispensed in milter (mL) (+++ + «5 digits plus decimal point) Ifo entry, the entire burette contents are dispensed ‘Theselected2.5mlL are dispensed. Theburetteisthen filed automatically. (‘Dispensing” as a method, see Section 9.1), 12 METTLER DL21/DL25Standby RUN L "WEIGHT" blinking RUN 4 "IDENT" blinking RUN tu "BUSY" blinking RUN zr "Busy" 4 "RESULT" ‘Appropriate configuration data are necessary for a successful titration. ‘The adaptation of these parameters tothe titration problems described in Section 5. It should be noted, however, that a major portion of all titrations can be carried out with standard values. 3.1. How to perform a titration Entering a weight value: Type in sample weight in g (or volume in mL if not already taken into account in the calculation constant CONC) and press [RUN]. If a balance is connected, the sample weight is displayed asa suggested value, but youcan overwrite. The transferred weight unit has to bee in gram. ‘Sample identification. (No request, ito printer, matrixprinter or lab infor- mation system is configured.) ‘As soon as the titration vessel containing the sample is attached to the titration head, the titration is started with [RUN], Warning: If the titration vessel is missing, splashing may ocour! ‘The titration is running. The stirrer is switched on automatically. Stirring speed is adjusted with the control knob at the right side of the housing. During the titration, the signal is displayed according to configuration parameter 1 in mV or pH. ‘The result is calculated as described in Section 6 and displayed. Example: Titration of 50 mL of a mixture of hydrochloric acid and acetic acid with NaOH, c = 0.1 mol/L, indication: DG111-SC glass electrode Titration number (set to 1 every time the 34 e-ti-ase6] instrument is switched on) ‘yn 20 (see page 31) ‘st result: hydrochloric acid content in mmol/L. 2nd result: acetic acid content in mmol/L With each titration the DL25/DL21 prints, next to the methods number, parameters 1 and 2, namely type (3) and control (1) and the date of the last modification (22-07-87). See also page 18 and 19. METTLER DL21/DL25 13,3.2 Printing out additional information ‘Additional information can also be printed out after the titration is ‘completed. However, this information can also be included in the auto- matic result record by appropriate selection of configuration parameters 1 and 7 (see page 29). The possibilty of subsequent printout is lostf the weight request for a new titration is initiated with [RUN], the configuration data are changed with [1] [MODE], or a new method is called up. Initial signal, consumption, equivalence point potential and half neutralization value Result of the last titration is displayed. ‘Same example as on page 13. TITRATION 2 Titration number METHOD 28 Method number WEIGHT & 2 | Weight IDENT 3589 5 Gonc mol/L 10050 | ‘denttication conet 20.00 | Titrant concentration Calculation constant START mv 259.8 | Initial potential of sample solution in millivolt (or pH) Bameon mr 3:0488 | 4st reagent consumption in mL. (without blank correction) Erie ee 2aal1 | Equivalence point potential in milivott (or pH) ° Half neutralization value in milivott (or pH) RESULT mmol/L 6.1301 | 1st result: HCl in mmovL. RESULT mi 3.0323 | 2nd reagent consumption eee 328:2 | Equivalence potential ® | Half neutralization value RESULT mmoi/h ‘6.0950 | 2nd result: Acetic acid in mmol Titration curve and 1st derivative ‘The titration curve andfirst derivative canbe printed withthe matrixprinter (but not with the GA42 printer). The curves shown on page 15 were reduced in size by 60%. The titration header (from titration number to CONST) which is also printed with every curve has been omitted. 14 METTLER DL21/DL25Titration curve Result of last titration is displayed. ‘Same example as on page 13 First derivative of the titration curve Result of last titration is displayed. ‘Same example as on page 13. oo ‘The derivative is shown on a logarithmic scale to allow even small inflections in the flat part of the titration curve to be seen. (Exception: segmented curves, see Section 14.2). METTLER DL21/DL25 15Table of measured values of the titration curve Result of the last titration is displayed, ‘Same example as on page 13. Volume Ast derivative Volume — Increment —_ Signal Signal change _ 1st derivative VOLUME DERIV. ‘VOLUME INCREMENT SIGNAL, S.CHANGR = DERIVATIVE Ani acre ot aL = av aval | 28566 -3 9366 00000 00000 289.5 Haso0 i200 24a 8 -a.6210 43660 5.4340 irsn0 S000 2a 3 caaleas ‘sae0e “5.8171 2.0000 25000 23710 8 Calas 2.9400 34000 22019 7 235.686 264008 =4 6458 2!5ro0 2300 22010 3 lyse : ara $7000 ate 2 “aelte9 41406 72 2.6700 18000 1 7 cs9'su1 4.2056 127 2ioese Hs00 a 8 “erle6e | i 3.0800 10500 a 8 mars 4.2650 w181, 31980 0500 ¢ 3 ceeas1 142 3.3180 12000 ° 63.739 Oey ] 3.4500 13500 4 8 ~85.780 4.3750 4 3.6150 16500 a 1 48.870 2 aos 18000 a o aegat 4 4268 a 4.0300 22500 1 2 36.568 4.4650 2 4.2800 25000 6 5 -33.870 8.64 4.5200 24000 7 @ “a2leze 4.5100 98 4.7700 25000 6 2 32.636 4.5558 6.22 £.0100 24000 2 4 caalaee al Bl2is0 20500 5 cae laze 4.6408 77d 54080 12000 2 8 aaleen 4.7166 7 «13 5.5800 14500 8.0 8 082 : slerso 2000 : ‘ 482 4.7556 5.78 Blrt00 aso = ‘ n9 42 5 5.9800 8000 7 & -110.50 pee 4 |S sie0 fan é + aslo 4.9856 29 sleto0 ‘san € 4 “eele3 i 5 10300 ‘5000 @ @ Zar9123 : 6.0900 ‘sano 1 8 lush 4 611500 ‘5000 3 2 “ez0.as 6.2100 ‘sano 3 é — Carelet 5 6.2700 6000 4 8 catelee 5 6.9350 05500 ° € — c24!30 = 614000 ‘ssn 4 8 elle: 5 6.4650 05500 @ S e1.et S 6.5300 09500 ® 6 “a51!86 : 6.6050 07300 3 "a “110,26 6. 6.6900 ost i 3 cn.da8 A 6!e100 12000 : co 768.212 Tan00 $9000 4 3 749.208 | 6 1.2080 20800 ° 1234567 : T6080 40000 3 8 =2a!s02 7 8!0550 45000 3 0 cares? ? sisss0 “30000 7 4 capita | 9.0580 $0000 5 eB. 14e 8. 9.5560 $0000 6 i 2812330 8 GA44 record (predecessor of GA42) Dot matrix printer record 16 METTLER DL21/DL25ao METHOD 4. Titration methods This section does only partly apply to the DL21 Titrator, which has no method storage facilities, except for one method. The DL25 allows storage of 50 different methods. The term *method” is defined in these Operating Instructions as follows: ‘A method comprises all the information necessary for the performance and evaluation of a titration. ‘Such information includes the complete configuration list (see page 18), the titrant concentration CONC (page 10), the associated constant for the standardization CONST REAG (page 32), the calculation constant CONST (page 30), the blank value BLANK (page 58), and for back titrations the excess BACK (page 55). These parameters, in particular CONG, are components of the method. If the same titrant iS used in several methods, CONC must be inputted separately inallthese methods The calibration data ofthe electrode (or buffer values with TAN/TBN) are valid for all methods. In other words, when the electrode data are changed, they are altered automatically in all relevant methods. Amethod with optimized parameters for the relevant titration is set up for every analytical procedure in an appropriate manner. This can be effected by changing the standard parameters (method 0) or by changing a similar method, TheDL25 stores 15 standard methods. They are describedin detailinthe ‘Application Brochure DL25. ‘When the instrument is switched on, the method last used is active. This also applies to a provisional method. 4.1 How to select, display, change and store methods Method n (0...50) is selected and can be used for the analysis. It can now also be cisplayed or altered. The instrument is inthe standby mode. The current method numberis displayed or aslongas the [METHOD] key is pressed, Method 12 is active, METTLER DL21/DL25 7By changing a configuration parameter or another critical parameter, ¢.9. CONC, the method becomes provisional. tan attempts made to display the method number, the display shows: Provisional method ‘The method is stored under this number (n = 1...50). Successful storage is acknowledged by an audio signal. ‘The number is occupied (occ = occupied) The old method is overwritten. If the current method should not be overwritten, abort with [RESET] and enter a new number. 4.2 Printing out methods and list of methods MODE ‘The current method is printed out. | metTHOD 29 Method number date O1-11-8e8 Date of last change cone moive const reag back mmol Blank mmo1 const CONFIGURATION TYPE CONTROL, PREDOSING BUR/MAXVOL STIR TIME ouTReUT sYsTem ST2O COND RINSE TIME RINSE DOS DOS Time OUDVOVOUSUNE PHO pH SLOPE mv¥7pH +1050 | Titrant concentration in moV/L +20420 | Constant for CONC determination +00009 | Excess for back titration “00000 | Blank value 02° | Calculation constant v2.0 | Software version Titration type Control and measured value acquisition Predispensing (or duration for pH-stat) Burette + maximum volume End point, threshold, dispensing or inactive Stirring time 00 | Result calculation + representation ‘System + peripheral units ‘Sample changer + conditioning Rinsing time Disp. time 1 for pump RINSE (or pH-stat time interval) Dispensing time 2 for pump DOSE Zero point of electrode assembly pH, -59.2 | Slope 18 METTLER DL21/DL25Inactive configuration methods are characterized by the absence of text in the method printout. The numeric value is then meaningless (e.g, ‘configuration parameter 5 in the above example). ‘The list of stored methods is printed out (with the exception of the standard method 0 and any provisional method). In addition to the method number, parameter 1 forthe titration type (type), parameter 2 for the control (control), and the date of the last change are printed out, METHOD no. tee control aate Methods36...50 are METTLER standard methods (date 00 00 00), which can at | : tol s130 15-10-08 | anytimebedeletedor moditied, suchas | Se s 1 bo.00 00 | Methods 46 and 47, =o 7030 2 ot-ti-ee | So oie 10290 00 00 | =o : 2 80 00 00 | a4 toot tet b6-09-88 ae soon 28a7_— G0 09 00 | as foot tit 29-10-88 as foot fet _—_60 80 80 | az 2001 201 00 00 00 ao us 2 00 80 80 Clearing methods ‘A method is cleared by loading method 0 (standard parameters) and storing it in place of the method to be cleared. To clear method 25, for example: METHOD Call up method o. Led Method number 25 is occupied. [25] [SAVE] Method 25 is cleared (comprises standard parameters only). METTLER DL21/DL25 19Adapting the parameters to the titration 5.1 Configuration A series of operating data must be entered in the DL25/DL21 for each titration. Those configuration parameters (1...7) which allow adaptation of the instrument toa titration problem as well as definition of the result representation are describedin detallon page 22. The parameters 9...C) ‘needed for operation with the sample changer are described on page 66. The present section describes the configuration parameters associated with the manner in which the system is set up. A listing is tabulated in ‘Appendix | or on the memo card. Entering the configuration Indicator lamps “WEIGHT” to "BUFFER B" are off. Recalling the configuration dialog. ‘The first number indicates the configuration parameter we are dealing with (1: titration type etc.). The last four digits represent the current data, ‘These data can now be simply confirmed or overwritten. The description, of the configuration data is summarized in Appendix I, page 108. ‘After an entry or to confirm an old value, press the [RUN] key. ‘The next parameter appears in the display. ‘The entire set of parameters can be run through several times. ‘The configuration dialog is concluded by pressing the [RESET] key. Please note: ifthe instrument cannot be configuredin ‘Standby’ with key sequence [1][ MODE], the crtical functions are blocked. These must first beunblockedwith key sequence [6] MODE] (see "Blocking andunblocking critical key functions”, page 9). 20 METTLER DL21/DL25Ps: Pe: Ps: PB: Pe: PB: moe none) gee A+0+ OoAs 5.2 System configuration (configuration parameter 8) Configuration parameter 8 contains details of the peripheral instruments (except balance and recorder) connected to the DL25/DL21 Titrator: Output devices: No output device Matrix printer (EPSON or compatible) to CL serial interface, 2400 baud, 8 bits, without parity check, at least 2K data buffer Lab data system to RS232C interface’, 2400 baud, 7 bits, even parity Matrix printer to CL serial interface and lab data system to RS232C interface, as above GA42 Printer to CL serial interface, 2400 baud, 7 bits, even parity Printer to CL serial interface and lab data system to RS232C interface, as above Active peripheral units to RS232C interface: (in these system configurations, a lab data system can be connected to the CL serial interface and configured in the same manner as a printer.) No sample changer ‘ST20A/ST20 Sample Changeris attached. It an error appears, the series is aborted and an error message outputted (ERRORS 30-33). ‘ST20A/ST20 Sample Changeris attached. I an error appears (ERRORS 30-33) the result is set to zero and the series run to completion. ‘The same as 2+ but with errors 30-34 the table of measured values is printed out to provide a clue to the cause of the error. DL25/DL21 Titrator to be configured (master) is connected to a second, ‘subordinate DL25/DL21 Titrator (slave) Device code A = 2, 3 or 4 (same code as for configuration of the ‘subordinate instrument) DL25/DL21 Titrator is subordinate to other active instrument (slave) Device code A= 2, 30r 4 METTLER DL21/DL25 24(Configuration parameter 1) Ptreee3 * Ifthe requestto-send line is not active, the data to be transferred are stored in the internal butter storage (ca. 180 characters) of the DL25/ DL21. If this is overloaded, the last string is replaced by CRILF. In addition to the reagent concentration CONC (see page 10) and calculation constant CONST (see Section 6, page 30), the proper selection of configuration data 1 through7 isimportantforthe achievement of correct results. Below you will find a detailed description of the possibilities provided by the DL25/DL21 With the configuration parameters 3,5, A, B andC the numberfora single positive value is with or without decimal point. These parameters are ‘marked in what follows with XXX.X. In certain parameters, each digit has its own particular significance. If in what follows only one digit is addressed, the other possible digits are ‘marked with a + Example: P1:++ 1 +. Of thefour possible digits, the 2nd digit fromthe right. of the parameter 1 is addressed. 5.3 Configuration parameters 1 through 7 Titration type Titration to the first equivalence point In by far the majority of cases, universal titration mode 1 can be used to achieve your objective. The titrant is addedin variable increments whose size depends on the dynamics of the signal change (dynamic titration). ‘At the same time, the data of this titration curve are checked for the presence of an equivalence point. if an equivalence point is found, the titration is stopped and the result is calculated. Only equivalence points with a 1st derivative greater than 20 mVimL are detected. Determination of the steepest jump * Titration mode 2 is used it the titration curve exhibits weaker inflections priorto the actual equivalence point, and determination of these inflections isnotrequired, orifthewholetitrationcurve sto be recorded. The titration is stopped when reaching the maximum volume (see page 28) Determination of all equivalence points * Titration mode 3 allow the determination and evaluation of all reco- gnizable steps of a titration curve up to the maximum volume. Caution: In this case, itis recommended to do a plausibility check by means of the titration curve or the table of values! 22 METTLER DL21/DL25PhieeeS Pt2e+7 Pites7 Pt:e+0- For the determination of the end point an iterative evaluation procedure is employed that utilizes the theoretical profile ofthe titration of a strong acid with a strong base as a model. i the titration curve shows major deviations from the typical S-shape, the iterative procedure can fail. In such cases the inflection point of the curve is determined by cubic interpolation. This is indicated in the result printout by the text «interpolation». The procedure also fails if the sign of the frst derivative changes immediately before or after the volume increment with the greatest slope. In this case the waming «deriv. sign change» is outputted inthe resutt printout. End point titration: positive end point (generally in pH)! negative end point (possible only with mV unit of measurement) lithe erid point of atitration is prescribedby a standard method orfor other reasons, titration mode 4 or 5 is selected, depending on the sign of the end point. The titration runs in a manner similar to the titration to an equivalence point but the size of the increments in the vicinity of the end point (end point + 1.5 + AE,,) (See P2: + X + +) is reduced to single pulses Of the burette. The end point is entered as configuration parameter 5 (page 28). Dispensing in mmol, when P7: + 9« - dispensing in mL. (see page 12) Determination of minimum Determination of maximum. The minimum/maximum determination is an ‘equivalence point titration with the special abort criterion of an absolute minimum or maximum (see page 53) Evaluation of segmented titration curves (see page 54) Measurement ‘The signalis measured.andrecordedinmV orwith 1: + + 19 inpH. Series. can also be measured and statistical evaluations performed. * The data storage can accommodate information for maximum 120 dosed increments. Equivalence points can therefore only be recognized and evaluated if they lie within the last 120 increments, Measured variable millivolt Measured variable pH: ‘There are various reasons for converting the measuring signal to pH: the initial pH may be of interest as analytical information and a printout is required (see page 29); or, for a given titration, the end point is predeterminedinpH. Inallcases, itisprerequisite that the calibration data of the electrode are determined automatically or inputted correctly (see Section 8, page 35). The titration curve should be scaled in pH units. METTLER DL21/DL25 23Plree2e Pires Pied PtOeee Ptrtesvor2err ‘Measured variable milivolt and determination of the half neutralization value (HNV). Measured variable pH and determination of the half neutralization value (HNV). High resolution Inatitration to the equivalence point, itis possible to have the increment in the steep region of the titration curve reduced to 1/1000 of the burette volume (1/2000 in an end point titration). Under standard conditions (60+), the increment does not fall below 1% of the volume already dispensed. With 5 mL, not below 0.05 mL; with 20 mL, not below 0.2 mL. ‘Thanks to the evaluation logarithm, the time saving in the majority of cases is considerable yet a very precise result is still obtained Standard parameter: The value of the thresholdwhich must be exceededbetore an equivalence point is recognized is 20 mV/ml. If the value of the first derivative increases twice and then decreases twice and if the maximums greater than the threshold value, an equivalence point is recognized. Tendency and threshold Inmost trations the equivalence point s clearly defined. Specification of the tendency (direction of the potential change in the region of the equivalence point = sign of the derivative) is unnecessary. With certain titrations, the direction can change during the titration and the tendency needsto be specified. Probably amore common reason tor indicating the tendency is that a value different from the standard value is required for the threshold (see below). Whenthe tendency andthreshold are specified the measuring signal unit (mV or pH) must be noted. Tendency and threshold should be set only in awkward situations since the conditions forthe equivalence point recognition are less strict than with the standard parameter. An equivalence point is recognized when the tendency is ‘correct, the value of the first derivative is greater than the threshold and the subsequent value of the frst derivative is smaller. Ptitere Positive tendency: Titrations with acids (mV), bases (pH), silver nitrate, oxidizing agents Pti2ere Negative tendency: Titration with bases (mV), acids, reducing agents 24 METTLER DL21/DL25XXX PUXere (Configuration parameter 2) 2:4 P2:08*X When specityingthe tendency, itis mandatory to also define the threshold in parameter 5. The threshold is used principally to prevent relatively ‘small disturbances in the curve being mistaken for an equivalence point. The firstderivative mustbe larger thanthe thresholdto ensure recognition of an equivalence point. Typically, half of the greatest value of the first derivative is advisable for the value of the threshold (see table of ‘measured values and 1st derivative of the titration curve). Threshold in mVimL or pHimL. (parameter 5) Special titration modes (X= 3...9) see Sections 13, 12, 15 and 11 ‘Measured value acquisition, time response and control Inthe standard case, regulation ofthe titrant addition by the DL25/DL21 {is dynamic and equilibrium controlled. This means that the titrant can be ‘added n variable increments (volume steps). Aconstant potentialchange AE... defined in parameter 2: + X + + is aimed for. This is achieved by varying the increment size. The minimum increment (AV,,,) is defined by parameter 1 (+0++ or + 1++); the maximum increment QV,,,.) by parameter 2 (X-+ +). ‘With large volumes the minimum increment could be greater than the maximum increment. The maximum increment has priorty. Before an increment is added, the measuring signal must have stabilized (show minimal dri, have attained equilibrium), parameter 2: (++ +X). However, the next increment is added atthe earliest after a minimum time (t.,) and atthe latest after a maximum time (t,,). The time window is defined in pparameter2 (++X-). Theincrements can, however, also be added at fixed time interval (parameter 2:+ + X +) i need be. Standard Inthe standard case, itis assumedthat both the response of the electrode and the reaction under study are sufficiently rapid, Equilibrium (Drift) The equilibrium conditions must be adapted to the reaction type. ‘With large jumps (100..500 mV), an equilibrium of 1 mVis or 0.5 mV/s generally sutfices. With small jumps, the drift should be limited to 0.25 or 0.1 mVis. METTLER DL21/DL25 25Parameter 2 Drift t imvis 158 0.5 mVis 15s 0.25 mV/s as 0.1 mVis 45s 0.25 mV/s, 6s 0.1 mVis 75s 0.5 mV/6 5 (oil) 18s Time condition ‘This parameters usedto define a time window (t,..t,.,)- The minimum time (t,.) is as well determined by the equiliorium Condition selected (see page 25). Proper choice of the time window not only prevents an crement being added too early (after only apparent attainment of the equilibrium) but also means that an unnecessarily long waiting time can be avoided. Virtually without exception, times longer than the standard times are needed only in redox titrations. For optimum selection of the two parameters equilibrium and time condition, please see Appendix F. For optimum determinaton of tse parameters for an unknown and ‘sensitive titration, itis advisable to connect a line recorder to the analog ‘output and to observe the course of the signal as a function of time in a preliminary experiment with stricter parameters. Parameter 2 tay aoe 60+ 15/S/45I675/18s 208 sete 6s 60s we2e 2s 120s wee 8s 24s onde 1.5/9/45/675/18s 908 “tan ffom the equilibrium condition is used if i is greater. In certain cases a fixed time interval is specified or recommended for other reasons. The equilibrium condition is naturally ignored in this case and can be set to zero (e.g. P2..50). A timed increment titration is performed, Parameter Time increment 655 as 96+ 105 a7 208 68+ 30s +69 90 s (oil titration) 26 METTLER DL21/DL25P2:+X+ P2:Xeee Ia fixed time increment is specified, the equilibrium condition (P2...X) is meaningless. It can be setted to zero e.g. (P2:...10). Control Inthe standard case, the DL25/DL21 Titrator controls the titrant addition dynamically to a set potential change AE, (also called anticipation) of 8 mV. In the case of a small, steep jump better control is achieved by lowering AE,,, to 4 mV. An acceleration can be achieved by raising AE... to 16 mv. Parameter2 AE,, +Oe8 8mV standard tee 4mV slower s2ee 16mV faster —_ (8 mV with blank determination) +B+5 30 mV oil titration (8 mV with blank determination) ‘Maximum increment (2 0+++t03 +64) ‘The standard value of the maximum increment (AV,,,, = 5% of the burette volume) assures optimum, rapid control in most appiications, especially with sigmoidal curve profiles. With titration curves which begin flat and then exhibit a large, steep jump, there exists a danger of overshooting. Asaprecaution, the maximum increment in this case is reduced to 2% of the burette volume or even less. Parameter AV, 0 5% standard tee 2% steep curve Qeve 1% Be 0.5 % Fixed increment (Kedereto9e es) Fixed volume increments are specified in various standards and applications. Parameter AV 0.1% of the burette volume 02% 05% 1% (0.5% in blank determination) 2% (0.5% in blank determination) 5% (0.5% in blank determination) METTLER DL21/DL25 ar(configuration parameter 3) PS: XXX.X_ (configuration parameter 4) PA: Kees Pa: XXX (configuration parameter 5) PE: XX XX Predispensing Before the controlledttration, the titrant volume inputtedin mlis dispensed in increments. This allows a reduction in the titration time. In general, a small predispensing is advisable (standard value 0.5 mL) since the electrode potential atthe start of the titration often changes drastically or is poorly defined. This inturn could cause detection ofa false equivalence point at the start ofthe titration. ‘The equilibrium conditions also apply to the predispensing, which occurs in three steps. P3 has a different meaning with pH stat (see page 47). Burette volume and maximum volume This is the abort criterion for titration types 2, 3 and 8 as well as the emergency termination for titration types 1, 4, 5 and 7 with error message 31. Input of the burette volume: 10 mL (ovo10) 0 standard 20 mL. (Dvg20) 1 5 mL (Dvg05) 2 1mi (ovaor) 3 Input of the maximum volume Pa: 10 10 mL standard Example: 1010 (20 mL burette) Maximum volume of 1...999 mL (whole mL only) End point (P1:+++4 or ++5) The end point potential is indicated in mV or pH. (The sign is defined by the titration mode, configuration parameter 1.) Dispensing (P1: 6 or 16) Dispensed amount in mmol or mL. (P7: +9 +) Threshold (P1: 1+ sand 3+ With special modes 1, 2 and: threshold in the derivative in mV/mL. or in pH/mL. 28 METTLER DL21/DL25(configuration parameter 6) PE:XXXX (configuration parameter 7) P7:+*XX PT7:O+0+ PIiteee P7:Qe05 P7:B+++to dere Stirring time Before measurement of the initial potential and before the start of the titrationa string timein seconds canbe selected. The stirringtime allows homogenization and dissolution of the sample. Representation of the results No curve Titration curve (pH stat: volume against time) 4st derivative of titration curve Titration curve and derivative pH stat: signal against time PH stat: volume, derivative and signal against time ‘No additional data Initial signal (unit pH or mV according to P1:++X-), consumption in ml Table of measured values + IS + V sree The table of measured values of the titration curve is printed out in numeric form. The raw resutt in milliter and the equivalence point potential in mV or pH are also printed out. ‘The records generated using these possi examples shown on pages 14 to 16. Allthe information, except the curves, specified here is also available at the RS232C datainterface ita lab information systemhas been configured (see page 21). Each protocol 2 ends with ASCII character CTRL Z (ASCII HEX 1A). fies correspond to the ‘Audio signal (beep) Keying, result, errors and inadmissible entries are signalled audibly. Only the result, errors and inadmissible entries are signalled audibly No audio signal. Complex calculations. Audio signal as 0 + « ‘system configuration (configuration parameter 8) (Gee page 21) Series titration (configuration parameter 9, A-C) (See “Series titration’, page 66) METTLER DL24/DL25 29(6. Result calculation In the standard case, the result is calculated according to the following formula: RESULT=CONST-_1__.v.. CONC WeGaT V = titrant consumption up to the equivalence point in mililiter (mL) V+ CONC = raw result in millimole CONST = calculation constant to convert the raw resutt into the desired unit. It can be determined in accordance with the table on page 31 Weight = weight (or volume) of the sample. For more complex calculations, see page 31; for the calculation of back titrations, see page 55. The blank correction is described on page 58. 6.1 Entering and checking the calculation constant CONST ‘Type in the value of the calculation constant and press [CONST] key. Without entry the stored value is displayed as long as the key is pressed. The parameters forthe result calculation and forthe units (P7:+ X ++) are described on page 31. For determination of the calculation constant CONST the appropriate formula for the desired result unit can be found in the following table. METTLER DL21/DL25Definition of the result unit Suitable selection of parameter 7: -X + - allows printout of the associated unit with the result. Parameter? -Resultunt CONST +008 none _freely selectable 1 mmol 4 ae % MI(10 +z) +3 ppm M- 1000/2 mg/g Mz mg/L M- 1000/(2 + U) gl Miz + U) g/100mL_ Mi(10+ z+ U) mmovL — 1000/(z + U) mL 1 M: molar mass of sample (g/mol) 2: equivalent number of sample (relative to titrant) U: volume of sample solution (mL). This quantity can also be inputted in place of the weight: weight = U. U does not then appear in the formula for CONST! 6.2 Special calculations Asa supplement othe standard content calculation, thereis a possibilty to calculate additional results automatically. They always follow the standard result, are characterized by a special name and are printed out without unit. The nature of the special calculation is defined in parameter 7. Reciprocal values, ratios of and differences between the last two results and actual value minus set value can be determined. These special calculations take results which are generated in a slave DL25/ DL21 also into account. Equation and meaning Parameter7 Designation in printout 1 / result = reciprocal value Bre reciprocal last result / previous result Aen last Riprev R previous result / last result Bees prev Rilast R last result ~ previous result bre last R - prev R previous result - last result Tees prev R— last R result ~ set value Bee R-set R Previous resutt + last result Ore prev R + last R METTLER DL21/DL25 31CONST REAG Note: The previous result must originate from the same determination as the last result. If itis generated by the “slave” it must be ensured that the “slave” uses the same constant and result unit as the ‘master’. If the penultimate result is missing, neither a special calculation is performed Nor a special result printed out. Inthe “actual-set” determination (8 «+ +) the back titration is not possible since the set value must be defined in the BACK memory. These special calculations are not possi in the determination of the p ‘andm value (see Section 11) orn the determination ofthe acid and base number (see Section 12. 7.__ The titrant concentration CONC. The titrant concentrationis storedinthe DL26/DL21 Titratoras parameter CONG in mole per liter (mol/L). A CONC determination automatically overwrites the old value. (For manual entry of CONC, see page 10.) When the burette is changed, a method with the correct value must be ‘employed. The titrant concentration is determined by a special titration ofa standard substance (primary standard). To obtain the automatic conversion of the titrant consumption to the desired concentration, a special calculation constant CONST REAG is used: -—1 |. WEIGHT CONC=CONSTREAG”—V \V = titrant consumption up to the equivalence point in milliliter (mL) ‘The calculation constantis determined according tothe following formula: M = slope. Stored slope is displayed, Entry or confirmation. The entered value is automatically set negative. Parameter number. PH, Conclude with [RESET] key. 36 METTLER DL21/DL25‘The electrode may be calibrated manually with other buffer solutions. In this case, pH, and the slope have to be calculated from the measured potentials of these buffer solutions using the following formulas: Potential asic Ho= PH ata ae ‘Slope Potentialaynens~ Potentialastere Slope = PHavtent~ PHasnere For the potential measurement, see page 8. A temperature correction is also performed manually. _ Dispensing an pores surementas@ These functions can be configured as a method so that they can be recorded on an attached printer/iab data system and automated with the ‘ST20A/ST20 Sample Changer. 9.1 Dispensing Configuration parameter 1: 6 or 16 Configuration parameter 5: dispensed amountin mmolormL (P7:+9+ Configuration parameter 7: 10 9.2 Measurement Configuration parameter 1: 9 or 19 Itis possible to measure the initial signal in mV or pH, exactly as ina titration. A pH electrode must be attached to the DL25/DL21 for this and. calibrated in the manner described on page 35. statistical evaluation of the measured potentials can be printed out with [9][RUN] if [SERIES][RUN] has been used. METTLER DL21/DL25 37=: 10. End point titration Inaddition toits universal method of an equivalence point finding titration, the DL25/DL21 Titrator also provides the possibilty of titrating to a preselected end point. This type of titration is used primarily if it is specified by a standard method (DIN, ASTM, etc). In these cases, itis frequently not a genuine equivalence point that is determined, but rather the titration is used to determine a characteristic value that has been definedby this standard method. (The titration curve does not necessarily ‘show an inflection point in the region of the end point.) The end point is generally specified as a pH value. To set up the DL25/ DL21 for the end point tation, the configuration list must be adjusted as follows (see also page 22): Configuration parameter 1 ++ 14 Configuration parameter 5 End point in pH Configuration parameter 1 is set to 4 or 5, depending on whether the end point has a positive or negative mV value. If necessary, the other configuration parameters must also be adjusted according to Section 5. ‘The end point titrationis aborted with error message 30 ifthe signal atthe star ofthe titration changes by more than 10 mV in the wrong direction. This can be prevented by configuring the tendency P1:1/2 + « ‘An end point titration is performed exactly as the titration described on page 13, buthere the end pointis printed out as an additional parameter. Example: Determination of the acid content of vinegar with NaOH, = 0.1 moll by tration to pH 9.5. Configuration: 14, 1, 0.5, 10, 9.5 (first 5 configuration parameters) Titration number Indication: DG111-SC glass electrode const =. 10 6.00 (see page 31) Result: g acetic acid/100 mL. vinegar 38 METTLER DL21/0L25jtectRsprey: Erno »| sone moist aed START ou state BLOPE mvyeH ‘aaa EP low pit can EP hign BH pe alae cn] BMV pw ‘as BR nigh pH mmoacE | 10.1 Two end points Titration to two preselected end points ‘This mode (P1:9 - 10 and 9 - 30) allows titration to two preselected end points. This titration can be pertormed only in the pH mode. In contrast to the usual end point titration, the two end points are not defined in the configuration but in the electrode data memory following the electrode calibration. All other possibilities of the titrator remain unchanged. Definition of the two end points ‘The function {1} [pH-CALIB] is called up in the standby mode. If the electrode data remain unchanged, they are confirmed by pressing [RUN] twice; the instrument then requests the two end points. The two end points are printed out subsequently in the configuration together with the electrode data How to perform a titration to two end points Example: Titration of phosphoric acid Titrant: NaOH, 0.1 mol/L. Consumption to pH 4.6 in mmol Consumption from pH 4.6 to pH 9.2 in mmol Ratio of the two results METTLER DL21/DL25 39‘Automatic printout of titration and 1st derivative by setting parameter 7t0+++ 3. | eerrarron * WEIGHT : Sone moist, 0938 Phat 40 METTLER DL21/DL2511. _p- and m-values ‘The determination of the p- and/or m-value in water and waste-water analysis is a special case of an end point titration. Here, the titrant consumption is determined in mmoV/L up to a pH value of 8.2 (p-value) and to a pH value of 4.3 (m-value). In titrations with hydrochloric acid the prvalue is also known as the phenolphthalein alkalinity or acid capacity K,,» whereas the m-value is called the total alkalinity or acid capacity Kz., (DIN 38409). Analogously, DIN 38409 refers to the m- or p- value obiained through titration with sodium hydroxide as the base capacity K,,0"Ky» Fespectively. (Depending on the application andsspecification, additional, special instructions are given. For example, the DIN standard 38409 stipulates addition ofacitrate-tartrate solutionin the determination Of Ka. Furthermore, there are other standards with slightly different pH values. ‘The DL25/DL21 determines both values automatically ithe initial pH lies ‘outside these limits. For such cases, connection of a printer or matrix printers indispensable as only the second result remains in the display. ‘The DL25/DL21 is set up for the p- and m-determination in the following ‘manner: Configuration parameter 1 deve ‘Switching to pH and specifying the end points to pH 4.3 and pH 8.2 is automatic. The other configuration parameters may be adjusted if necessary as described in Section 5. Parameter 8 in particular has to be set to 8 + for the unit mmolL. In the analysis of water, we recommend thatthe predispensing (configuration parameter 3) be setto zero. Thetwo end points can be modified in the way described on page 39. In the CONC determination described in Section 7, the initial digit 4 of configuration parameter 1 is ignored. Consequently , for this purpose, the titration can be defined with + (and the configuration parameters 2 and, if required, 5)! The blank value correction of the p- and m-values is possible, as well as the backtitration. No half neutralization values (HNV) are calculated When the p- and m-values are determined, there is no difference in procedure from the description on page 13. METTLER DL21/DL25 aa | peer 8 cone moi7h caste START pH ees pHO pH 6.764 BLOPE mv/pi ee M-POINT pH 4.300 PlporNT pH e200 RESULT mt 2600 P-VALUE mmoi/t RESOLT mt as20e BAVALUE mmoi7t) Example: Determination of the acid capacity of alkaline effluent. Configuration: 4011, 2, 0, 10 (first 4 values) Titration number Indication: DG111-SC glass electrode Sample: U = 50 mL. Const. ‘00 =20 (see page 31) p-value or K,,.. in mmol. m-value o K,, in mmol Corresponding method METTLER DL21/DL25[zi Acid and base number TANWTENT Determination of the acid or base number in accordance with the ASTM procedure D664/D4739 or D2896 is not easy to carry out using the standard tration. In the DL25/DL21 therefore, special titration functions are available which allow the analysis of petroleum-based products according to the standard method. The TAN/TEN determination requires Connection of aprinter or matrix printer as several resuits are determined automatically Butter potentials Accordingto the ASTM D664/04739 standard, ifno recognizable inflection point is found the consumption up to the specified potential of two butter solutions is evaluated. Inthe TAN/TEN determination with the DL25/DL21 Titrator the function [pH CALIB] thus has a different meaning; instead of the electrode Parameters for a pH measurement the potentials of the two specified butfer solutions are measured in mV and stored. The determination is performed and checked exactly as described in Section 8. Concerning acid and base number acidic butter potential basic butfer potential BUFFER my Result printout of buffer potential measurements if the DL25/DL21 is configured for TAN/TBN determination several TAN/TBN ~ methods are stored, the buffer potentials willbe the ‘same for all these methods (only DL25). According to the ASTM D2896 standard, only inflection points in the titration curve are evaluated. To preventthe evaluation to butter potentials, the first butfer value is thus set to 0 by manual entry (see page 36). Since the DL25/DL21 switches off the TANTBN titration mode for a CONG determination automatically, access to the buffer potentials is possible only after titration of a sample or after determination of the butter potentials with [1] [pH CALI} METTLER DL21/DL25 43‘Acid number: Base number: SAN TAN ACID NO. ‘SBN TEN BASE NO. Result determination Al results are printed out in mg KOH per g sample either needed to neutralize acidic components (SAN, TAN, ACID NO.) or equivalentto the basic components (SBN, TBN, BASE NO.) Strong acid number, determined from the consumption to acidic butter potential Total acid number, determined from the consumption to basic buffer potential ‘Acid number, determined from the consumption to detected inflection point. Every inflection point found is evaluated. ‘Strong base number, determined from the consumption to basic buffer potential Total base number, determined from the consumption to acidic butter potential Base number, determined from the consumption to detected inflection point. Every inflection point found is evaluated. SAN, TAN (and SBN, TEN) are results that are determined only at specified butter potentials in accordance with ASTM D664/D4739. Contrary to the other titration modes the titrator calculates in the TAN/ ‘TBN mode the consumption from the start of the titration to the potential Or inflection point Halt neutralization values (HNV) are not calculated. After the titration has been evaluated, the TAN or TBN value is displayed. Without butfer potentials, the last acid or base number is displayed. Blank value determination The determination of the bank value of the particular solvent mixture in question is performed using the same titration method (same configuration). With butter potentials not set to 0, the consumption is evaluated up to the buffer potential designating the total acid number or total base number. Otherwise, consumptiontothe 1st equivalence pointorthe steepestjump is evaluated METTLER DL21/DL25Configuration parameter 1 3003 Configuration parameter 2 2347 7090 12.1 Titration according to ASTM D664/D4739 Setup This sets the calculation constant CONST to 56.1 and the signal unit to mV automatically. The buffer potentials must be measured periodically with fresh buffer solutions. In the CONC determination, the initial digit 3 of configuration parameter 1 is ignored and the final digit 3 automatically set to 1 (titration to first equivalence point). The configuration must not therefore be changed, Meaning Dynamic equilibrium titration with Maximum increments of 1% of the burette volume (0.1 mL with 10 mL. burette) ~ potential change anticipation: 30 mV — admissible drift 0.5 mV/6 s — minimum waiting time 18 s — maximum waiting time 90 s Timed increment titration with ~ fixed increments of 1% of the burette volume (0.1 mL. with 10 mL. burette) time interval between increments: 90 s Parameter The above parameters correspond to the conditions required by the standard. Naturally, they can be adapted for preliminary experiments or special applications. ‘The remaining configuration parameters are adjusted if necessary as described in Section 5. The predispensing (configuration parameter 3) is normally set to zero. ‘The titration is stopped if the butter potential designating the total acid or total base number is exceeded and the signal derivative falls below 500 mV/mmol (= 50 mV/mL) at CONC = 0.1 mol/L). METTLER DL21/DL25 45Configuration parameter 5 Configuration parameter 1 3001 Configuration parameter 2 327 ‘Threshold ‘The equivalence point recognition can be influenced by a change in the threshold. The first derivative must be greater than the threshold in the region of the equivalence point to ensure evaluation of an equivalence point Blank correction Only those results whose consumption is greater than the consumption upto the total acid or total base number are corrected by the stored blank. (SAN or SBN are thus not corrected.) Statistics. ‘The TAN or TBN value is used as result for the statistics. 12.2 Equilibrium titration according to ASTM D2896 Direct titration ‘The calculation constant CONST is set to 56.1 and mV assigned to the signal unit automatically. ‘The first butfer potential must be set to Oto prevent evaluationof thetitrant consumption up to the butter potentials. ‘The final digit of configuration parameter 1 has the meaning described on page 22 and occasions the end of the titration after the equivalence point has been found (1) or when the maximum volume is reached (2, 3). In the CONC determination, the initial digit 3 of the configuration parameter 1 is ignored. The configuration mustnottheretore be changed. The recommended equilibrium conditions forthe TAN/TEN determination. in the case of parameter 327 correspond to the 5 mVimin (0.5 mV/6 s) required by the standard. The potential change aimed for is 30 mV (or 16 mV with parameter 2: 227). The remaining configuration parameters are adjusted it necessary as described in Section 5. The predispensing (configuration parameter 3) is. normally set to zero. 46 METTLER DL21/DL25Configuration parameter 5 Threshold ‘The equivalence point recognition can be influenced by a change in the threshold. The first derivative must be greater than the threshold in the region of the equivalence point to ensure evaluation of the equivalence point. Back titration ‘The back titration is referred to in the ASTM D2896 standard. The DL25/ DL21 Titrator allows back titration with both the equilibrium titration and the incremental titration. The first buffer potential must, however, always be set to zero. Inafirst step, an excess of the 1sttitrant is added as described in Section 17. Titration is then carried out with the 2nd titrant to the first detected inflection point only (Par. 1: 3001). (13. pHstating ‘The pH stat titration or pH stating is used to keep the pH constant. Of prime interest here is the time dependence of the titrant consumption. In addition to measurement of the total consumption of titrant this method ‘can be used to determine the mean consumption (mL/min) within a selectable time window. Before the actual pH stating, the pH must in many cases be adjusted before the sample is added. This can be achieved using a pretitration or by means of a normal end point titration, Inthe pretitration of pH stating the end pointis reached quicker than inthe end point tration since in the vicinity of the end point the decrease in the size of the volume increment to be dispensed is less. The pretitration is usually controlled with the same parameters as the end point titration, Pretitration andpH stating employ the same control parameters. Only the ‘equilibrium (dri) and the time condition of configuration parameter 2 have an appreciable influence on the control of pH stating. The time condition mustbe selected such that, of he time window is as small as possible. The time t.,, isthe earliest time the nexttitrant increment can be ‘added when the signal differs from the end point (set potential) of the pH stating. For pH stating therefore, only the parameter values P2:++ 01 and P2:++ 02 are appropriate. METTLER DL21/DL25 a7Parameter PIS +++ PUTeee PL6ere PUB eee 8: XXXX P3:0 B: XXXX B:0 ‘The set potential change AE,,,(P2: + X++) has no appreciable influence ‘onthe control of the pH stating as long as the deviation fromthe set value is less than 1.5 + AE,,.. But with a greater AE,, the pretitration can be accelerated. ‘The control of the pH stating can also be adjusted by use of different burette volumes (e.g. 5 mL) andlor by dilution of the titrant. it must be ‘noted, however, that after the discharge of one complete burette stroke somewhat more than twenty seconds elapse before the burette is refilled and the pH stating can be continued. Meaning pH stating with pretitration, positive tendency pH stating with pretitration, negative tendency. In afirst step the pH of the solution is adjusted. The sample can then be added. Recording of the consumption does not begin until after addition of the sample. PH stating, positive tendency pH stating, negative tendency Duration of the pH stating in minutes and seconds. Apredispensingis not possible in the pH stating. BH stating with no time limit, Abort effected with [RESET] Time interval for the storage and printout of the data in seconds. With a time interval < 4 seconds, irregularities may arise since the time for the addition, measurement and printout of the data is too short. ‘Automatic dispensing with the rinsing pump at the ST2OA/ST20 Sample ‘Changer is thus not possible. ‘Storage after addition of every increment. METTLER DL21/DL2513.1 Data storage and printout Any number of data sets can be printed out online. After 119 data points a data reduction is effected in the data memory, i.e. every second entry is cleared, ‘The message «Data Points > 120» appears on the printer. Itaninterval time has been configured, after every data reduction this doubled when entered in the data memory. It no interval time has been configured, each measured value is entered even after a data reduction. is ‘The table, which can also be printed out online, ie. during the pH stating, shows all important values: time, volume and consumption during the time interval (increment), the signal of the electrode (pH) to check the quality of the pH stating and the derivative of the consumption against time as the frequently most important result. The derivative is a direct ‘measure of the reaction or dissolution kinetics under investigation by pH stating, 13.2 Time window Many pH stat applications need as result the reaction rate within a certain time interval. The time window can be defined before or after the titration with 1[pH CALIB}. The time window is thus not part of the method. It must be reentered ifrequired when one pH stat methodis replaced by another. ‘The values last inputted for a time window remain stored. 13.3. Entering the time window ‘The zero point of the electrode assembly pH, is displayed. (Electrode calibration, see Section 8.) The electrode slope is displayed. The start of the time window can be entered in minutes and seconds. The end of the time window can be entered in minutes and seconds. ‘The end of the time window can be entered, METTLER DL21/DL25 4913.4 How to perform a pH-stat titration With pretitration ‘The desired method is recalled and in a first step a beaker with solvent but without sample is attached to the titration head. The pretitration (a ‘normal end point titration with the same parameters as the pH stating) is started with [RUN]. After attainment ofthe end point no result appears but the burette is set to zero and the sample data (WEIGHT and IDENT) are requested. The “BUSY” lamp begins to flash, indicating that the weighed sample can now be added. The actual pH-stating is started with [RUN]. The pH-stating with pretitration can only be performed manually and not with the ST20A/ST20 Sample Changer . Example: Determination ofthe enzyme activity of pancreatic lipase at pH 8 by pH-stating with sodium hydroxide 0.025 mol/L, temperature: 41 °C. Configuration: 5114, 1101, 5, (Par 1. Titration number ), Par B: 15: WEIGHT we Indication: DG111-SC, combined glass electrode done morse, ‘S3s00 | Sample: enzym suspension (~1 mg Enzym) memos’ ert S090 CONST = M- 100/5 for a result in activity units/g. Enzym = mL, NaQH Brant ot e223] (0.025 moll) + 100/min. SEOrE mer “| Result: titrant consumption in mL and activity units/g Enzym RESULT me +-9800| Result: mean consumption within the specified time window Time window secre Result: mean consumption of NaOH in mLimin. eee | mrman | For the interpretation and evaluation of a pH-stating, data other than those provided by a standard tation are of interest. These data can be taken from the table of measured values online (Par 7:+ 3) or printed out afterwards with [7] [RUNI. one rs = strain o 50 METTLER DL21/DL25Three different curve plots can be configured or subsequently printed out with (XJ[RUN]. The consumption is usually shown as a funetion of time (P7:++* 4, +*+3 or [5] [RUN]) ‘The first derivative of the consumption as a function of time allows assessment of the reaction or dissolution kinetics (P7: ++ + 2, +++ 3 or [6] IRUN) METTLER DL21/DL25 51For a check on the quality of the control with the selected control parameters, information is provided by the plotof the signal as a function of time (Par7: +++ 4 0r{6] RUN) or online witha line recorder connected to the analog output. With parameter 7: + + 5 all curves are printed out. pH stating without pretitration It the pH of the solvent, the medium or the substrate is correct or noneritcal, there is no need to perform a pretitration, For work with the sample changer the pretitration must be switched off. Some other means must be used to preadjust the solvent to the correct pH. The same also applies if the sample weight has to be determined by back weighing. 52 METTLER DL21/DL25Configuration parameter 1 (14. Special evaluation procedures ‘The evaluation procedure of the DL25/DI21 can no longer be used if no S-shaped curves are obtained. Two additional methods are available in ‘such cases to calculate the titrant consumption up to the equivalence point. These titrations are performed in accordance with the description in Section 3.1 14.1 Determination of the minimum/ maximum of a titration curve ‘The result of this determination is the minimum (maximum) calculated fromthe data points of the titration. This titration mode finds principal use in turbidimetric surfactant determinations with photometric indication. Meaning Determination of the minimum; standard threshold 20 mV/mL. Determination of the minimum; threshold according to parameter 5 Determination of the maximum; threshold according to parameter 5 ‘The titration is aborted after recognition of the first equivalence point (minimum or maximum), ‘A minimum (maximum) is recognized as an equivalence point if the following two conditions are fulfilled: = Afteraminimum(maximum) the measuredpotential value mustincrease (decrease) twice, — Before the attainment of the minimum (maximum) the value of the first derivative of the titration curve must be greater than the value of the threshold at least once. Adaptation of the threshold allows suppression ‘of small discontinuities in the titration curve that can lead to false ‘minima (maxima). E —vV —vV All other configuration parameters have their usual meaning (see Section 5.2). A half neutralization value (HNV) is not calculated. METTLER DL21/DL25 53Configuration parameter 1 0++8 14.2 Titration curves with linear sections (segmented curves) Various methods of indication (including photometry, conductometry and ‘amperometry) generate titration curves with linear or approximated linear sections (segmented curves). A special evaluation procedure has been developed for these curves. For an exact determination ofthe equivalence point tis essential that these curves have not only linear sections but also a distinct break in the region of the inflection point. Meaning Evaluation segmented curve. No specific tendency, threshold in mVimL? ‘or pHimL? according to parameter 5 Evaluation segmented curve. Tendency positive, threshold in mVimL? or pH/mL? according to parameter 5 Evaluation of segmented curves. Tendency negative, threshold in mV/mL? or pHimL? according to parameter 5 ‘The titration is aborted at maximum volume. ‘The threshold and tendency have a meaning different from that in other titration modes. The tendency (direction of the potential change in the vicinity of the equivalence point) relates not to the titration curve but to the first derivative. The threshold thus relates to the second and not the first derivative. The second derivative must be greater than the preset thresholdintheregionof the equivalence pointin order that an equivalence point can be recognized. AS an aid, for each equivalence point found the maximum value of the second derivative (max deriva) sprinted outin the record. The printout of the 1st derivative ofthe titration curve has a linear scale of the ordinate. All other parameters have their usual meaning (see Section 5.3). Itis advisable to perform the titration with constant volume increments (P2:X +++, X=4, 5,6, 7, 8,9). For S-shaped curves the titration data are evaluated using the standard procedure. This does not use the experimental points of the titration curve butrather the dataof the first derivative calculated from such points. Ahalf Neutralization value (HNV) is not calculated. E| E| E| METTLER DL21/DL2515. Back titration Inaback titration, the first step involves addition of an excess of titrant to the sample. In the second step, the unreacted portion of the titrant is determined with the aid of a complementary tant. The content of the sampleis givenby the difference inthe added milimoles of thetwotttrants, used, This methodis used, for example, ithe sample reacts only slowly with the titrant and this reaction can be accelerated by addition of an excess of titrant. The extraction of the components to be titrated out of the sample matrix can also be accelerated in some cases. An additional application ‘example is the determination of nitrogen by Kjeldah's method in which the ammonia released is steam distilled into a sulfuric acid trap and determined by back titration with sodium hydroxide. ‘The DL2S/DL21 calculates the result of a back titration (i.e. if BACK #0) by the following formula: RESULT = CONST: t+ BACK — V+ CONC BLANK) 1GHT BACK — = _ Excess in millimole V=CONC = Raw result in millimole BLANK — = Positive blank value in millimol (see Section 18) Ifthe result unit mlis configured (P7: +9 »)inaititration, this configuration must also be employed for the blank determination and the entry of the excess. Back titration is not possible in the CONC determination (see page 32). Use ofthe titration mode toall equivalence points (configuration P1: + «+ 3) is also senseless and can lead to calculation errors. Inthe DL25/DL21 the excess can be added using the dispensing function IBURET]. The amount is entered in the parameter storage BACK in ilimol and taken into account automatically in the calculation of the titration result. A practical approach involves the use of two burettes, the tips of which can both be inserted into the titration head. The change in reagent can then be accomplished simply by sliding the burettes in the holding rack and locking in place by means of the knurled screw. ‘The excess can also be added automatically with a second DL25/DL21 (slave) or with a dispenser (only with ST20A/ST20 Sample Changer) METTLER DL21/DL25 55‘MODE 15.1 How to determine the excess The amount of excess in millimoles is found from the concentration in millimole per milliliter and the volume dispensed in milliliters: BACK = CONC + Volume (mmol) (mmovimt) (mL) For value entry, see page 7. ‘The excess can also be determined automatically and stored. This involves dispensing, in aditferent mode, of the required quantity of the 1st titrant with the dispensing function [BURET] after determination of the titrant concentration by the method described in Section 7: Correct CONC value of 1st titrant isin the parameter storage. The lamp above BACK (and BLANK) indicates that the determination involves the excess to be dispensed. (I dispensing is not required at this time, no burette is placed over the drive.) Volume to be dispensed is entered in milliter (= 20 mL). The required volume is delivered. ‘The value calculatedin mmol (CONC +20) s printed out and stored in the parameter storage BACK. 15.2 How to perform a back titration ‘The concentration of the 2nd titrant must now be stored in the parameter storage CONC. The burette containing the 1st tant is in the drive. The excess dispensedusing the dispensing function [BURET] (seepage 12). Next, the burette above the drive position is changed and the actual titration performed as described in Section 3, page 13. It it is desired to enter the sample weight and identification before dispensing the excess the entries shouldbe made with [SERIES INPUT] The titration is started with [SERIES RUN] after the excess has been dispensed (see also Series titration, page 62) METTLER DL21/DL25“WEIGHT” blinking aa ] “IDENT” blinking RESET| v [BURET| + "BUSY" blinking Cron] “RESULT” Standby ‘The correct amount of excessis stored in BACK, concentration ofthe 2nd titrant in CONC. The sample number is displayed for one second. ‘The weight is entered or transferred from connected balance. ‘Sample identification. (No request, if no printer, matrix printer or lab information system is configured.) {st titrant in drive position, sample at working place. ‘The same volume as that in the excess determination is entered for the ‘excess in terms of burette volume, ‘The excess is dispensed. ‘Change to 2nd titrant. ‘The titration is performed with the data entered as “series sample". ‘The titration is running, ‘The result of the back titration is calculated using the formula on page 55 and displayed. Example: Determination of potassium aluminum sulfate content Back titration of aluminum with EDTA and zinc sulfate, 0.1 mol/L. Configuration: 1, 3, 0.5, 10 (first 4 values) Titration number Indication: Amalgamized DM141-SC silver electrode, 3 drops Hg-EDTA, 0.05 mol Butter: pH 4 CONST = M/10 = 47.439 page 31) Dispensed excess EDTA for back titration, Result in % METTLER DL21/DL25 3716. Blank” In certain titrations a small part of the titrant consumption up to the equivalence or end point is not due to the sample component under investigation but to the sample matrix (all other components), the solvent cr in general to the sample preparation. in such cases, an exact result requires correction by the so-called blank. Such a blank correction is carried out automatically if the blank in millimoles is stored in the parameter storage BLANK. The result calculation described in Section 6 is then carried out according to the modified formula: RESULT=CONST-__1___. (V+ CONC- BLANK), WEIGHT V+CONC = Raw result in millimot BLANK — = Positive blank in millimol METTLER DL21/DL25Standby move] [| RUN i "IDENT" blinking RUN | v "BUSY" blinking _RUN uN | "Busy" 2 "RESULT" ‘Standby 16.1 How to determine the blank ‘The DL25/DL21 Titrator supports the blank determination and storage by means of a special operating mode. This involves a titration to the first equivalence point. Any configured predispensingis suppressed. Maximum 8 mV is allowed as set potential change. In a titration with fixed volume increments work is performed with increments of maximum 0.5% of the burette volume. A sample is titrated that should contain all sample ‘components except that under investigation. For example, a sample with the known content zero is prepared in exactly the same manner as the normal samples. ‘The blank is equal to the raw result of the blank determination: BLANK = V+ CONC. ‘The lamp above BLANK indicates that a blank determination is being performed, No weight entry. Insert identification number. Attach titration beaker with sample for blank determination to titration head. ‘The titration is running. ‘The displayed result is the blank value in millimol or, if configured, in milter, which is simultaneously stored as BLANK. The blank titration can be performed as a series titration. Here the value of the last determinations entered each time as BLANK. ifa subsequent statistical evaluation is performed with [9][RUN), the calculated mean value is entered and printed out. METTLER DL21/DL25 59Example: Determination of the blank value of 50 mL solvent (ether! ethanol 1:1)for the ttration ofthe free fatty acids in sunflower oil with KOH in t-butanol, ¢ = 0.1 mol. Configuration: same as for titration of the sample (see below) Titration number Indication: DP550 Phototrode, phenolphthalein Blank in mmol or mL Example: Determination of free fatty acids in sunflower oll with KOH in butanol, ¢ = 0.1 mol/L, taking into account solvent blank. Configuration: 1, 2, 0.5, 1 (first 4 configuration parameter values) Titration number Indication: DP550 Phototrode, phenolphtalein Conversion to mg KOH/g: CONST = M(KOH) = 56.1 Blank in mmol Result: acid number in mg KOH/g sample. 60 METTLER DL21/DL25‘Standby SERIES) INPUT £ “WEIGHT” blinking RUN + “IDENT” blinking RUN x + "WEIGHT" blinking RESET] Standby The DL25/DL21 possesses a memory for 60 series sample data (sample ‘weight, identification number and resutt. It is thus possible to weigh a series of samples before the fistttrationis started. Thisis of special value ifallthe samples have to undergo analysis pretreatment simultaneously, Examples: Solubilization, extraction, saponification by boiling. Using a sample changer and a dot matrix printer, the titration of the whole series may be automated. 17.1 Sample entry ‘The sample number is displayed for one second. ‘The weight is entered or transferred from a connected balance. ‘Sample identification. (No request, if no printer, matrix printer or lab identification system is configured.) ‘The next sample number is displayed for one second, The weight of the next sample is entered. The sample entry is concluded. Entry record for the first 3 samples. ‘Sample entry is not possible while the series titration is running. But itis possible, with the key [SERIES INPUT], to cause the DL25/DL21 to interrupt the process at the end of that particular tiation. Then an entry may be made. METTLER DL21/DL25 et"BUSY" blinking RUN v “Busy” L "BUSY" blinking RUN [oe t Standby [FivRatron 17.2 Howto perform a series titration When a sample changer is attached processing of the entire series is, started automatically with [SERIES RUN]. No other manipulations are necessary, Without sample changer: The titration is started as soon as the titration beaker containing the first ‘sample is attached to the titration head. The titration is running, Warning: I the titration beaker is missing, splashing may occur! The result is printed out. The next sample is attached to the titration head. If no printer, matrix printer or lab information system is configured, the instrument displays the result after the titration in the standby mode. The next sample is started by pressing [SERIES RUN] again. ‘The instrument also returns to the standby mode atter the final sample has been titrated. Example: Determination of the NaCl content of mayonnaise with 0.1 AgNO, c= 0.1 mol/L; Stirring time 60 seconds Configuration: 4, 1, 0.5, 10, 0, 60 (first 6 configuration parameter values) Indication: M141-SC silver electrode CONST = M/10 = 5.844 (see page 31) ‘% NaCl in sample 1 % NaC! in sample 2 % NaCl in sample 3 62 METTLER DL21/DL25Eo 17.3 Statistical evaluation With series titrations, the DL25/DL21 Titrator allows statistical evaluation of the results. A result (the last in the case of several results) is stored for every series sample. The statistical evaluation is performed over all analyzed samples of a series (maximum 60). The results remain stored even after the statistical evaluation. But if the method is modified, replaced by a different method (DL25 only) or if a series blank or CONC determination is performed, the results memory is cleared automatically. ‘As a consequence, statistical evaluation of results of different or altered ‘methods is not possible. With series without data input, statistical evaluation is performed over an Unlimited number of results since the individual results are not stored in this case, but rather the mean value and standard deviation are continuously updated. Checking the results With [2][SERIES INPUT] all results contained in the series sample storage can be printed out. Clearing the results All sample data and hence also all results are cleared with [9] [SERIES INPUT]. Selective clearance of all samples with resultis performed using [7SERIESI[INPUT]. Inthe event of a power failure, however, all sample data are preserved. With [1] [SERIES INPUT], asingle resutt, for example a maverick, can be cleared selectively by overwriting the result not wanted forthe statistics, with [0] (only in series with data input). This is done in the way described onpage 65. The instrument confirms the deletionby the printout: "Sample deleted’ METTLER DL21/DL25 63statistics NUMBER s How to perform a statistical evaluation Aseries of several titrations is complete, the instrument is in the standby ‘mode. The statistical evaluation is started with [9] [RUN]. Break and errors Ia series is interrupted during a titration with RESET the resutt of this sample is setto zero. If an error occurs the results also setto zero. Result zero (0.000) is ignored in the statistics and the message: “Sample deleted” appears on the printer. Method No 2 Number of results nos Mean value with unit 201745 Standard deviation with unit 4.2020 Relative standard deviation in % tent = List of resuits METTLER DL21/DL257) [eERES INPUT “IDENT" blinking "WEIGHT" blinking 17.4 Checking and alteration of series sample data ‘Sample data already entered can be displayed and written over: The sample number is displayed for one second. ‘The sample weight is displayed and can be written over. ‘A.quick press of the [RUN] key causes the sample number to be raised directly. ‘The identification is displayed and can be written over. ‘The next sample number is displayed for one second, Printing out the contents of the series sample storage Keying in [2[SERIES INPUT] prints out the series sample storage contents (see page 63). SERIES INPUT METHOD SAMPLE NO RESULT ent wercHT 1 3s 2.3089 4 ° 216889 5 ° 218003 6 s 2 Clearing the data of a sample 10 is entered instead of the sample weight, the data of a sample are cleared. This is possible, however, only at the start and end of a series. Clearing the contents of the series sample storage Entry of [S[SERIES INPUT] clears the contents of the series sample storage completely. Note particularly that the stored results of titrated series samples are also cleared. METTLER DL21/DL25 CFConfiguration parameter 9 eet PB: moe Bee oeNe XXe0 17.5 Series titration without sample entry Set up: ‘This turther simplifies the series titration fixed volume samples are used and if an identification entry is not needed. The sample volume in this ‘case is taken into account in the calculation constant (see page 31). The results are numbered consecutively. ‘The series titration s started with [SERIES RUN], This continues as long as there is no break in the sequence of sample beakers on the sample transport Itis possible to add additional sample beakers to the end of the series at any time. 17.6 Rinsing, dosing, titration and conditio- ning with the ST20A/ST20 Sample Changer ‘Summary of the configuration possibilities with the ST20A/ST20 For more details about parameter 8 see also page 21. The sample changer is attached. In the event of an error the series is aborted with an error message. ‘The sample changer is attached. In the event of an error the result is set to zero and a waming appears on the printout. The series is continued. ‘The sample changer is attached. In the event of an error the result is set, tozero and a warning appears. The series is continued. Further, itvalues are available, a table of measured values is printed out Series titration with sample data entry (for maximum 60 samples) Series titration without sample data entry, unlimited number of samples Series ttrationwithout sample data entry, butwith result storage (maximum, 60 samples) Conditioning atter N titrations Conditioning time XX in units of 10 seconds (10...990 s) 66 METTLER DL21/0L25PA: PB" PC: Rinsing time, with pump at connection “RINSE in seconds Dosing time, with pump at connection “RINSE* in seconds Dosing time, with pump at connection “DOSE” in seconds “Parameter B has a different meaning in pH-stating (see page 47) Rinsing For accurate work with the sample changer, the carryover of residues from one sample to the next must be prevented. This is achieved by intensive rinsing f burette tips, electrode and stirrer inthettitrated sample lowered to the middle position before transport of the next sample. The total rinsing time with the pump connected to the “RINSE” socket is, definedin configuration parameter A in seconds (rinsing time = A seconds). ‘Additional cleaning is possible by use of wash samples as “conditioning samples” (see page 68). Dosing ‘The ST20A/ST20 allows three independent dosing operations before the actual titration: Dosing of solvents Dosing of solvent to dissolve or dilute the sample. Here, the solvent dispensed through the rinsing channels is the same as that used for rinsing after the titration. The quantity tobe dosed is defined by the dosing time in configuration parameter B* in seconds (dosing time = B seconds). Dosing of additional liquids Either a pump connectedto the “DOSE” socket or adispenser connected to the DIN socket can be used for this dosing operation. (Simultaneous ‘operation of the two types of connection is also possible.) In the case of the pump (or magnetic valve), the quantity to be dosed is defined by the dosing time in configuration parameter C in seconds. The precise volume is set onthe dispenser andthe unit simply receives a start signal. ‘An additional possibilty involves use of a second DL25/DL21 for precise dosing, forthe adjustment of a desired pH value (end point titration) orfor a first titration. For a description, see page 12 and 71 METTLER DL21/DL25 orConditioning ‘The use of conditioning samples has several purposes: Conditioning of the electrode at the end of a series. Conditioning of the electrode after each batch of N samples. e.g. in nonaqueous titrations the operational efficiency of the glass electrode should be preserved using an aqueous conditioning sample, Cleaning of electrode, stirrer, etc. ina suitable wash solution. Conditioning samples are marked by red stoppers on the sample table. ‘Any number of conditioning samples can be distributed. When a conditioning beaker is recognized in place of the next sample, stirring is performed with this beaker at the titration station during the conditioning time and rinsing is then carried out as normal ‘The conditioning time XX is defined in units of 10 s in the two lefthand digits of configuration parameter 9 (XX ++). Conditioning time = XX + 10 seconds (10...990 5). To save space onthe sample changer, configuration parameter9 canbe defined with -- N+ such that conditioning must be performed after every batch of N samples. I now there is no conditioning sample marked with a red stopper in the next position, the sample changer searches back to the last conditioning sample. Itthen continues with the next sample. The only condition which must be observed isthe following: There mustbe no ‘empty positions between the last titrated sample andthe last conditioning sample. If this were the case, the error message “ERROR 41” would appear and the sequence be aborted. Itthe table has to rotate backto a conditioning beaker, no rinsingis carried out after conditioning since the beaker could be overtilled. Chronological sequence of all functions of the series titration with the ST20A/ST20 Start of the series titration at the DL25/DL21 (master). + Printout of the sample data of the 1st sample. {t conditioning beaker in next position: After rinsing into the last beaker, the sample changer transports the conditioning beaker in which conditioning is carried out during the configured stiring time to the titration head. METTLER DL21/DL25Ht sample in next position: After rinsing into the last beaker, the sample changer transports 1st sample to the titration head. Rinsing agent is dosed during the configured time B. Stirrer starts Second DL25/DL21 (slave) performs the configured tiation or dosing. it the second DL25/DL21 is configuredfor a lab data system, all output data (without curves) are printed out via the master. Dosing agent is dispensed during the configured time C. Dispenser is started. Master DL25/DL21 performs the configured titration. It conditioning beaker in next position or sample counter indicates that ‘conditioning is required: ‘Sample changer transports conditioning beaker tothe titration head after rinsing into the titrated sample. If sample in next position ‘Sample changer transports next sample to the titration head atter rinsing, ate. METTLER DL21/DL25 6Standby ee Cz MODE 17.7 Manual operation of the ST20A/ST20 Sample Changer The sample changer functions can be activated individually via the keyboard of the DL25/DL21 for setting up and checking purposes. The ST20A must be configured in the active method for this. Operation mode for manual operation of the ST2OA/ST20. The function is called up by means of the numeral keys. The DL25/DL21 remains in this operating mode until aborted with [RESET] Incase of an error press [RESET] twice. The individual functions. Pump “RINSE” is active as long as this key is pressed. Pump “DOSE” is active as long as this key is pressed. Further, the dispenser is started. Functions 1 and 8 serve to fill or rinse the lines. Pump RINSE” is activated for A seconds (A = the time selected in ‘configuration parameter A) Pump “RINSE” is activated for B seconds (B = the time in configuration parameter B). Pump “DOSE is activated for C seconds (C = the time selected in configuration parameter C). Dispenser is started. Functions 1...6 can only be executed ifthe lift is in the upper or middle position, ‘With each press of the key, the if is moved one position: bottom — top > middle -» bottom. With each press of the key, the turntable is moved forwards one position. ‘With each press of the key, the tumtable is moved backwards one position, For functions 8 + 9, the lit is moved to the lowest position beforehand, 70 METTLER DL21/DL25We Remote control Full remote control of the DL25/DL21 is possible by use of a master control unit, All key functions are controllable via the RS232C interface using the commands shown in the table below. For output of the dot matrix printer record via the RS232C interface (excluding graphical representation), see System Configuration, page 21 Each remote control command blocks the whole keyboard since no provision is made for parallel operation. On the other hand, the keyboard canbe freed again by remote control. Remote control commands (except status request, RESET and, in part, RUN) are accepted by the DL25/ DL21 only in the standby mode (exactly analogous to the keys) Key Command —_ASCIll HEX ') 0t09 0109 30t039 : . 2E cE c 43 RESET L 4c BURET /mL M 4D pH-CALIB N 4 RUN ° ar MODE H 48 CONST 2 495A) SERIES INPUT J 4A SERIES RUN K 48 BLANK ez 455A) BACK a 47 5A2) ‘CONG oz 44542) CONST REAG FZ 465A) SAVE P 50 METHOD az 515A) Unblocking Keyboard = Y 59 ‘Simulated power up ' at Status request 2 3F ') serial 7 bits ASCII 2400 baud 1 parity bit, not checked 1 stop bit Other than the stated characters are ignored *) 2 characters command METTLER DL21/DL25 n72 Lamp Status ‘Standby ° WEIGHT 1 blinking 9 IDENT a blinking 40 Busy 4 blinking 12 BUFFER A 16 blinking 24 BUFFER B 32 blinking 40 BUFFER A&B 48 Display test 119 “Not Standby” 3) 64 lame Standby mode, the actual function, isnot, however, signaled by a amp. (For example, the burete is being flea after completion of a METTLER DL21/DL25Connection of a second DL25/DL21 ‘The DL25/DL21 can be used as master for remote control of a second DL25/DL21 used for dispensing or to perform another titration with the ‘same sample. The function ofthe second DL25/ DL21 (slave) isperformed before the titration of the master. Master: Configuration parameter 8 20+ Slave: Configuration parameter 8 0+ 220+ 23 (itadot matrix printer is attached to the slave) For manual entry on the second DL25/D121, the keyboard mustbe freed with [RESET] on the master OL21/DL26. If the outputs of the second DL25/D121 are tobe printed out on the printer or matrix printer connected tothe master DL25/DL21, the RS232C interface and the printer must be centered in configuration parameter 8 of the second DL25/DL21 (25 and 21, respectively, see page 21). The printing of further information (see page 29 and following) with the second DL25/DL21 is possible only ona printer connected to this instrument. Remote control ofthe master DL25 by amaster computer's possible. The adapter cable (order number 23826), for example, can be employed for the connection. Alllines which begin with DCn (n=2, 3 or 4, corresponding to configuration parameter 8) received by the computer are commands to the second DL25 and should be ignored. Connection of a sample changer ‘The DL25/D121 can control a sample changer in addition to a second. DL2s/DL21. Remote control of the master DL25/ DL21 by a master computer is possible also in this case. If the DL25/DL21 controls a sample changer only, the adapter cable (order number 23826) can again be used. For remote control of a master DL25/DL21 wich controls the sample changer anda second DL25/DL21, a special adapter cable mustbe employed. All lines beginning with DCn (n = 1,2, 3 or 4, corresponding to configuration parameter 8) received by the computer are commands to the sample changer and the second DL25/DL21. They should be ignored, METTLER DL21/DL25 7374 Testing of the interface For testing of the interface and a better understanding of the set of ‘commands for the remote control of the DL25/DL21 one can use either ‘@ ANS/-terminal or an appropriate terminal program. Example of such a program in BASIC on an IBM PC. 100 CMg="comi" 150 CLS: PRINT "Terminal Emulator” 160 OPEN CM$+":2400,¢, 7,1, c80,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, TS; | 205 IF ASC(TS)=13 THEN PRINT CHRS (10); | 210 IF (256-LOF(1))=0 GoTo 170 | 220 P§eINPUTS (1, #1) 230 IF ASC(P$)<>10 THEN PRINT PS, 235 IF ASC(P$)=13 THEN PRINT CHR$ (10) 240 Goro 170 METTLER DL21/DL25“Appendix A: aE specifications | Measuring System End point indication _ potentiometric. voltametric (with DK102A, M142) colorimetric (with DPS50, DP660) ‘Amplification range +3000 mV Resolution 0.1 mV, 0.001 pH Accuracy 40.02 pH within the pH range 0-14 Measuring input DIN 19262 jack and 4 mm banana socket Input resistance 25-10 Q, protected up to 1000 V Offset current <1 pA (20°C) ‘Analog output for 44 potentiometric recorder Dispensing Interchangeable burettes equipped with maximum 2 Burette volumes, 4,5, 10 and 20 mL Resolution 1/2000 of burette volume =05,25,5 010! Acouracy better than 0.3% for consumption greater or equal 30% of burette volume Delivery time minimum 20 s for one burette volume Filling time 208 Keyboard Splashproot Titration types To first equivalence point Equivalence point corresponding to steepest inflection in tration curve All equivalence points To preselected end point To two preselected end points pH-stating TANITBN (acid or base number) according to ASTM D664, D2896 p-and m- value Reagent addition: dynamic or with constant volume steps Measured value acquisition: equilibrium controlled or timed increment METTLER DL21/DL25 75Result calculation ‘Automatic conversion of titrant consumption relative to sample weight to yield the content in the desired unit Evaluation procedures for S-shaped titration curves (standard), for ‘curves with minimum/maximum and for curves with several sections. Back titration Blank correction Reciprocal result ‘Sum of two results Ratio of two results Difference between two results Result minus set value Series sample storage ‘Sample weight, sample identification and results for 60 samples Data storage ‘Storage for 120 points (volume and signal) Method storage (DL25 only) Storage for 50 methods Auxiliary functions Determination of titrant concentration with automatic evaluation Blank determination Excess determination for back titration pH calibration (2 point) Dispensing Stirring Measurement Propeller stirrer ‘Automatically switched, variable speed adjustment 0..-8200 RPM Connection possibilities for peripheral instruments Balance Bit-serial current loop data interface for all Mettier-Toeldo balances with CL data output. Printer ‘Same interface for alphanumeric Mettler- Toledo GA42 printer (20 characters per line). Dot matrix printer ‘Same interface for Epson-compatible matrix printer (with graphics facilities) with buffered RS232C interface (minimum 2K butter) via conversion cable. METTLER 0121/0125Laboratory information system (LIMS), ‘Computer ‘ST20A/ST20 Sample Changer ‘Second DL25/DL21 ‘Computer and second DL25/DL21 and ST20A/ ‘sT20 Optional RS232C (DCE) data interface, also for remote control. Connection also via optional RS232C (DCE) data interface. (ST20 is the name of the older model.) Connection also via RS282C (DCE) data interface and adapter cable for remote control by first DL25/DL21 (master-slave operation), Connection via special adapter cable. Additional specifications Plastic parts Width x depth x height Weight Ambient temperature Polyester (housing), polypropylene (titration stand) 380 x 350 x 270 mm approx. 5.5 kg 10.95 °C Power supply connection 100/120 V 230/240 (+10%/-15%) Power consumption * For instruments conforming to IEC-348, see Appendix F. 50/60 Hz* 600mA 300 mA METTLER DL21/DL25 7Appendix B: Standard equipment and optional accessories Standard equipment Equipment supplied Order No. 1 Basic DL25 or DL21 instrument incl. spare fuse 1 Operating Instructions German 704093 English 704094 French 704095 1 Memo card German 704079 English 704080 French 704081 1 Application brochure German 724105 English 724106 1 Power cable Neutral 87576 FRG 87925 USA 88668 ‘Switzerland 87920 1 Interchangeable burette 10 mL see Accessories incl. burette piston, piston rod burette holder, tip holder, dispensing and suction tubes, tube of silicone grease 1 Propeller stirrer, complete 23890 1 Titration stand, complete Dv7oe 1 Coaxial cable for electrodes with plug-in head ‘89603 SC DIN 50 cm 1 Philips screwdriver No. 2 73072 78 METTLER DL21/DL25Optional accessories Interchangeable burettes Interchangeable burette, complete mt Sm. 40 mt 20 mt. comprising: 1 L brown glass bottle Burette holder Piston Dv905 Dva10 Dve20 Piston rod for Dv905 for DV910 for DV920 ‘Stopcock parts (1 of each) Valve disk (min. order quantity: 5) Rubber washer Follower cam ‘Threaded ring Light protection tube Dispensing tube with siphon tip 700m Suction tube 830m Order No. v4o1 Dv90s Dvo910 Dvg20 71296 29645 23710 23711 23712 23636 23636 23636 101003 25737 25715 25716 23644 25687 25688 METTLER DL21/DL25Siphon tip set set of 5 Gasket for 1 L brown glass bottle Tip holder for burette tip Stopper ST 14.5 min, order quantity: 5 Set of labels for DV905 Dv910 Dvg20 Order No. 23240 23981 23960 23646 25703 25704 25705 NOTE: The 1 mL burette differs from the other three burettes. If you order the DV401 you will receive a set of Operating Instructions with details of the appropriate spare parts. For titrants that have to be protected against moisture or CO, you can order a drying tube with holder, for titrations that you have to run under certain gas atmosphere a gas inlet, and for bottles with a different screw thread the appropriate adapter. Burette incl. stopcock Smt 40 mL. 20 mt Dispensing tube 1m Gas inlet 25724 25708 25725 25961 29721 METTLER DL21/DL25Drying tube Drying tube holder Molecular sieves 250 g Adapter Bottles of Merck, D Fisher, USA Titration stand, complete, comprising: spacing ring threaded ring clamping ring knurled screw (for securing the titration arm) Stopper ST 14.5 min. order quantity: 5 Stopper ST 7.5 min, order quantity: 5 Electrode holder min. order quantity: 5 Tube of silicone grease Rinsing unit, complete, with titration head insert and stoppers {or titration head openings not in use 1 Set of stoppers for rinsing unit Order No. 23961 23915 1478 2374 23787 Dv702 23842 23455, 23845 25650 23451 2452 25654 71300 23821 101280 METTLER DL21/DL25 882 ay Disposable titration beakers, 100 ml. polypropylene Titration vessel, glass, 80 mL. Titration vessel, 100 mL. polypropylene, red Titration vessel, glass, 250 mL. Titration vesel 150 mL, brown glass Titration vessel 5 - 20 mL, glass Thermostatable titration vessel, glass Plastic cover for titration vessels Heat exchanger for thermostating particularly with sample changer incl, adapter with taper joint Polarization current source METTLER DL21/DL25 set of 1400 set of 20 set of 1400 set of 10 set of 25, set of 16 Order No. 101974 101446 25777 23515 23828 23516 23517 101448 23834 DK1028,NON NANA N Combined pH electrode for acid-base titrations (up to pH 14) in aqueous solutions. Combined pH electrode for small volumes in small tiation vessels, in aqueous solutions Combined glass electrode with movable sleeve frit for titrations in nonaqueous solutions ‘Combined glass electrode with movable sleeve frit for titrations in aqueous solutions ‘Combined glass electrode with sleeve frit for titrations in aqueous solutions. Combined platinum ring electrode for redox titrations Combined silver ring electrode for argentometric and complexometric titrations Cables for electrodes with plug-in head: Coaxial cable with DIN connector SC-DINS0_50 cm Coaxial cable with DIN connector SC-DIN100 100 cm. Double-pin platinum electrode for voltamettic titrations Banana plugs, cable length 50 cm Banana plugs, cable length 100 cm Phototrode (incl. power supply unit, cable length 70 cm) for color-indicated titrations Transmission measurement at 555 nm Transmission measurement at 660 nm Order No. Da111-sc DG101-sc Da@113-se Da114-sc Da115-Sc DM140-Sc DM141-sc 89603, 89604 DM142 DM142/100 DP550 METTLER DL2¥/DL25Propeller stirrer complete with 2 sti Stirring rod Micro stirring rod (for titration vessel 29516) Peripherals ‘Alphanumeric printer (cable not included) Connection cable for GA42 printer Conversion cable dot matrix printer (with RS232C) — DL25 (CL) Mettler-Toledo balances with data output Connection cable for AE balances Connection cable for PM, AM, AT balances Connection cable for Titrator <-> LC-CL. cable LC-CL cable for AB, PB, PR balances Order No. 23830 101229 655073 Gaa2 17842 23827 106090 229130 METTLER DL21/DL25Order No. [===] _ Converter cable for SARTORIUS balances 106028 “> RSICL-CUIRS ‘Sample changer for 20 samples (100 mL) or ST20A with a turntable for 14 samples of 250 mL. (optional accessory) Miscellaneous | Microfuses, 400 mA, slowsblow, for 20-240 V", 51967 S| sot of 3 VWs Microfuses, 800 mA, slow-blow, for 100 - 120 V", 20182 Oe sot of 3 (ae-~| Data output RS2320 (DCE) 23955 Connection cable for RS2320 interface male female 59342 male ~ male (enclosed with ST20A 59348 ‘Sample Changer) ‘male (25 pin) — female (9 pin) 59759 ‘Adapter cable DL25 (RS232C, DCE) - DL25 23826 Sy (AS232C, DCE) and ST20 Sample Changer & (AS232C, DTE) & ( ) * For instruments conforming to IEC-348, see Appendix F. METTLER DL21/DL25 85Appendix C: __ Installation procedure Checking the operating voltage Before switching on the system for the first time, make sure the voltage indicated on the yellow label (atthe power cable socket) concides with the voltage of the local powerline. The power voltage is also indicated on the model plate next to the power cable socket. Changing the operating voltage To adjust the operating voltage of the instrument, proceed as follows: Disconnect power cable! Place instrument on table as shown in ilustration and loosen the seven sorews (1) with a Philips screwdriver. Carefully remove bottom from upper housing and place it down on the table. The transformer is built into the upper housing. Change cable (2) to the pin which is labeled with the local power line voltage. Before reassembling the instrument, make sure connectors are all well connected and positioned, When reassembling the instrument, make sure knob (3) used to adjust the stirer speed fits into the cutout of the upper housing made for this purpose. If an RS232C data output is built in, it must be inserted in the ‘upper housing with a slight pessure. Screw in the seven screws (1), Using a screwdriver, pull out the fuse holder (arrow) from between the power switch and the power socket, and recheck the nominal current of the microfuse: 100-120 800 mAslow-blow* Order No. 20182 220-240'V 400 mAslow-blow" Order No. 51367 * For instruments conforming to IEC-348, see Appendix F. 86 METTLER DL24/DL25Setting up the titration system How to equip the titration head Loosely attach the titration head (4) with the knurled screw (6) to the Titrator DL25/DL21, position it unti the torsion-protection cam snaps in, then tighten knurled screw (5). Insert stirrer drive (6) fromthe top and stirring rod (7) fromthe bottom into the center opening ofthe tiation head (4) and attach them to each other. Insert burette tip (8) into one of the small openings and electrode (14) in ‘one of the large openings nextto the stirrer (6). Whenever possible, they should be placed opposite each other (better control conditions), Close off unused openings with stoppers. Place clamping ring (10) on threaded ring (9) and screw onto titration head (4) by turing twice. Press titration beaker upwards against the inside of the titration head and secure by screwing threaded ring (9) not too tight. Set a relatively high stirring speed, but avoid splashing, Assembly of rinsing unit Remove sample beaker and stirrer. Unscrew threaded ring (9) completely, pull clamping ring (10) and spacing ring (11) out ofthe titration head (4). {tis imperative that unoccupied openings in the rinsing unit (12) be closed with stoppers (12b) in accordance with the procedure described below. Place rinsing unit (12) in titration head in a manner such that the Connecting tube (12a) is inserted into the opening with raised edge. ‘Secure connecting tube by means of knurled nut (19). Connect rinsing-water bottle to connecting tube (12a) with tubing. Secure tube endings with locking plastic ring. Place clamping ring (10) on threaded ring (9) and screw onto titration head Unoocupied openings must be closed with stoppers (12b) at all costs! For fitting, place stopper on the forefinger with the edge facing upwards, Positionthe stopperbelow the openingto be closed and press againstthe stopper with the metal rod (12c) (see illustration). Guiding the stopper in this manner, press it into the opening, Forremoval, simply press out the stopper (12b) with the metal rod (12), METTLER DL24/DL25 87Connection of stirrer, electrode and line recorder The electrode cable plug (15) is plugged into either the DIN jack (16) or the sockets (17). ‘The stirrer cable plug (18) is plugged into the cinch socket (19). The banana plugs of the recorder cable are connected to the banana sockets below the power plug Attaching the sample beaker ‘Turn threaded ring on bottom of tration head slightly to the left loosen), and remove beaker with trated sample. Press titration beaker with next ‘sample upwards against the inside of the threaded ring and manually turn ring to the right until the beaker is attached. Avoid fixing the beaker, especially brown-glass beakers, too tightly as because the clamping ring then loses its shape. As a consequence, it may then become difficult to remove the beaker. To restore the clamping ring to its original shape, unscrew the threaded ring, remove clamping ring and carefully stretch it by hand. 88 METTLER DL21/DL25e@-: o—: 2 4 b Installation and maintenance of the interchangeable burettes Inserting the piston ‘a. Piston (1, 2 +3) and piston rod (4) for a 10 mL or 20 mL burette. Insert O-ring (1) inthe groove of the lower part of piston (2) and screw together with piston head (3) and piston rod (4). b. Piston (1, 2 + 3) and piston rod (4) for a 5 mi burette: Lay O-ring (1) inopeningoffpiston head (3);itdoes not sit int ts final position until you srew in piston rod (4)with lower part of piston (2) a. Slide the piston carefully into the burette cylinder so that the broader part of piston rod (1) remains visible. 'b. Press the burette onto burette holder (2) thus positioning the piston exactly (3). Note: Before you slide the piston of a 20 mL burette into the cylinder, moisten it slightly with titrant or deionized H,0: this lessens the considerable friction between piston and cylinder. Inserting the burette Slide the burette on the holder rack of the DL25/DL21 with the knurled screw facing ight. Secure the burette after it has snapped in by turning the screw clockwise. METTLER DL21/DL25 89‘Assembling the burette ~ Lay gasket (2) on bottle (1) and screw on burette holder. = Insert either stopper (5) or a drying tube. Caution: If you use a stopper as protection for the reagent, always use the stopper with the flat sides (see ACCESSORIES: Order No. 26646) otherwise an underpressure will build up in the bottle. — Push suctiontube (5) into the bottle - slide the red PE tubing over iting (6a) as kink protection - and screw it into the left connection on the burette head. Screw dispensing tube (6) into the right connection and place other end in the tip holder (7). = (8)isthe burette head that you can remove when cleaning the cylinder to avoid smearing the inscription on label 9). (10) isthe light protection tube. lt you replace or clean parts of the stopcock (11, 12, 13 + 14), unscrew threaded ring (11) and remove follower cam (12), rubber washer (13) and valve disk (14). — Place the rubber washer on the follower cam followed by the valve disk. You can then lightly smear the surface of the valve disk with silicone grease. Press the three parts from below ontothe ceramicdisk of the burette with cam (15) pointing outward (centered exactly). Take special care to ensure that cam (15) is positioned correctly, otherwise the burette could be damaged! Invert the burette, mount the threaded ring and screw it on while holding the follower cam. 90 METTLER DL21/DL25METTLER DL21/DL25Cleaning the burette parts Depending on the titrant, you should clean the burette cylinder, piston, stopcock and tubing relatively often. ~ Slide the burette off the ttrator, invert it and carefully take out the piston; this causes the burette contents to flow out through the suction tube. Turn the stopcock to the left through 90° and any liquid in the stopcock will flow away through the dispensing tubing. Then disassemble the burette completely and clean each part — Depending on the contamination caused by the titrant, rinse cylinder ‘and tubing with acid or deionized H,0 then with ethanol and finally dry the parts with compressed air. ~ Never attempt to remove any crystalsin the cylinder by scratching with a hard object! — Never put the parts in a drying oven at a temperature greater than 40°C! — Never place O-rings and rubber washers in organic solvents! Notes for burette parts - Grease the piston rodwith silicon grease toprotectitagainst corrosion. — Replace the piston i it leaks or is badly scored at the edge. Replace the rubber washer of the stopoock fairy often as it becomes hard and brittle with time. — With titrants that can crystallize out in the tip of the dispensing tube (KMnO, or KOH/MeOH) and which you do not intend to use in the near future, itis best to empty and clean the dispensing tubing: Unscrew it at the connection and the titrant flows out automatically. Then also ‘check the threaded connection and wipe off any drops! 92 METTLER DL21/DL25Peripherial instruments In order to record results automatically, a printer (METTLER GAd2: RS232C interface) or a dot matrix graphics printer with at least 2K Byte buffer can be connected to the data output of the current loop data interface. If the dot matrix printer (e.g. EPSON) is equipped with an RS232C- interface, connection to the CL intertace of the DL25 is achieved with the conversion cable listed under Accessories. When a balance (e.g. METTLER AE160 with Option 011) is attached to the titrator the sample weight can be transferred directly to the titrator. The ‘weight unit must be set to gram. Caution: The data output of the attached balance must be configured as follows: 2400 baud even parity send continuous ‘These settings must be checked according o the Operating and Installation Instructions of the balance and corrected if necessary. The weight unit must be set to gram. ‘The balance and the printer or matrix printer are connected to the same socket of the CL interface. (The connector of the balance cable is equipped with a socket which can accommodate the connector of the printer.) ‘AnS232C (DCE) data output for connection of aprinterorcomputercan be installed in the DL25/DL21 in a simple operation at any time. Order number see Appendix B, page 78. METTLER DL21/DL25 93‘The pin assignments of the coupling are as follows: Coupling: 25 pin sockets, female Signals: Meaning Pin 1: ProLGND protective ground Pin 2: TXD transmit data data from computer Pin 8: RXD receive data data to computer Pin 4: RTS Tequest to send _—is detected Pin 5: CTS clear to send DL25 always on receive Pin 7: SG signal ground Pin 8: DCD Data cartier detect Reception It the request-to-send line is not active, the data to be transferred are stored inthe internal butter storage (approx. 180 characters) ofthe DL25/ DL21. If this is overloaded, the last string is replaced by CRILF. With the connection of alline recorder, the electrode signal can be plotted as a function of time. In certain cases, this is extremely useful for interpretation of the electrode behavior or the reaction rate. Switching on ‘The power switch is located at the rear of the instrument. For control purposes all display elements light up for about 2 seconds when the instrumentis switched on. it dot matrix printer has been configured, the date is displayed and requested after this display check (see page 7). METTLER DL21/DL25Err o OD 6 m Ss 8 a a cy mm 6 Cy m [Appendix D: Errors and malfunctions | Error messages Any error message must be cancelled by pressing [RESET] to continue working. Instrument error Please note the appearance of this error code. It it appears repeatedly, the instrument should be serviced. Microprocessor Program storage Methods storage. After [RESET], standard values are inserted (DL21). Methods 1 to 35 are erased and methods 36 to 50 are loaded again with standard parameters (DL25). Signal digitaization. Electrode faulty or not property connected. Burette drive faulty, dispensing tube blocked. ‘Stopcock drive faulty, heavy incrustation in stopcock region, stopcock mounted wrongly. Error in communication with external instrument Receipt of external data too fast (option RS232C) ‘Asecond DL25/DL21 configured, but not connected, not switchedon, not configured correctly or faulty. ‘Sample transport configured, but not connected, not switched on or faulty, No result transfer between slave and master. METTLER DL21/DL25 95| haa Operating error Value entered is too large. No series sample data available. Performance error Signal change in opposite direction Evaluation: no result. In tiation modes 1, 2 oF 3, predispensing may be too large. Evaluation: no measuring data available. ‘Tendency or threshold wrong (titration types 1 +++ and 2+), Electrode calibration: Wrong buffer solution (butfer potentials differ by less than 100 mV) or electrode in poor condition (severe signal noise, drift after 1 minute greater then 0.25 mV/S s). ‘Storage for series sample data full (max. 60 samples). Numerical value not representable. 96 METTLER DL21/DL25rr Err @ a Err Err Err m7 cy aa aaa raz Taz Ta) TZ] Err 75 aT aim cy s Errors in connection with ST20A/ST20 Sample Changer No sample or inappropriate fill height. Avoid fill heights between 75 and 85 mL. (small beakers), as well as between 200 and 225 mL (large beakers). No conditioning beaker found (see also Err 40). Lift is not, as expected, in the lowest position. Lift is in the lowest position. ‘Short circuit at dosing pump input. Short circuit at rinsing pump input. Intemal short circuit. Data transmission error. Check cable and connectors, ‘Tumtable is jammed. ‘Turntable is not positioned. Lift is jammed or faulty. Light barrier of the fit faulty. Undefined lft position, Power supply disturbance. Errorin electronics. On recurrence, the ST20A/ST20 is to be maintainded by your nearest service facility. METTLER DL21/DL25 7Faults, possible causes, remedial action Malfunction Possible causes Remedial action ‘No dispensing. Titrant leaks Burette tip blocked. Clean burette tip. from stopcock or piston. Tum follower cam to correct Follower cam mounted position with cam facing wrongly on burette stopcock. outwards (see page 89). Wrong potential or pH value, —_| Electrode faulty. Check reference electrode ‘endpoint titration suddenly gives wrong results. Calibration fautty solution and liquid junction (frit oF joint. GAA2 printer or dot matrix printer prints incorrectly or not at al Printer is not switched on. Printer is not specified properly in configuration parameter 8 Printer faulty. Switch on pr ter, For correct configuration, see page 21. GA42 printer prints smaller Printer roller diy, Clean printer roller with characters, paper transport ethanol. imregular. — DL25/DL21, printer or balance | Break in power supply. Check power cable, can not be operated voltage and fuses. Weight from connected balan- | Balance is over — or under- Balance with empty ce is not displayed by DL25/ | loaded while switched on. weighing pan switch on again. DL21 on weighing, Printer prints sHHHHH# in Numerical value not Eg. in the case of pH: non-sen- place of numerals, presentable. sical electrode calibration data In titration mode 1: Electrode poorly Clean electrode and Titration is aborted too soon —_|_ maintained or fautty diaphragm, refill reference and gives a result which is solution. too low. Predispensing insufficient. Choose a predispensing Threshold too low. Electrode signal fluctuates (noise), but electrode in large enough to avoid discon- tinuties in titration curve. Select titration type 2 and working order. adjust maximum volume accordingly. In blank determination Blank very small and cannot Examine table of measured Value found is much too high, | be determined, values or titration curve to ‘no inflection point. check plausibility. METTLER DL21/DL25Note: If the instrument is not used for a period longer than one month, all stored information (parameter values, configuration, methods) may get lost. In such a case all this information must be reentered manually. You are thus strongly advised a) to switch the instrument on for at least a few hours every month during lengthy breaks in operation andb) to document all stored methods. METTLER DL24/DL25 99[Appendix E: Glossary (Technical terms) | General terms Equivalence point (also known as end point, neutral point) The point at which the same (equivalent) number of particles of the titrant has been added as there have been particles to be determined in the sample. Itis defined by the equivalence point potential EQ. POT and the equivalence volume V (titrant consumption up to the equivalence point) In most cases, the equivalence point coincides approximately with the inflection point ofa titration curve. Half neutralization value ‘The hal neutralization value (HNV) or point of halt neutralization is equal to the pH at haif the consumption to the equivalence point. HNV is used for the characterization of the titrated compound. For medium strong acids and bases itis close to the pK and can be used for its calculation. Indication ‘A method used to follow the course of the titration and to detect the equivalence point. The most important methods are potentiometric, voltametric and photometric indication. Measuring chain In the case of potentiometric indications, the titration procedure is followed with the signal of an electrode assembly consisting of an indicator electrode (glass electrode, ion selective electrode, metal electrode) and a reference electrode. Generally, single rod electrode assemblies (combination electrodes) are used. ‘Standard solution solution of precisely known concentration used to standardize atitrant. Titration (also known as volumetric or tirimetric analysis) Quantitative chemical analysis in which the volume of a reagent of {definite concentration needed to react quantitatively (stoichiometrically) with the analyte is determined. From this volume, itis possible to calculate the content or the quantity of the substance under investigation in the sample. 100 METTLER DL21/DL25Titration curve Graphical representation of a titration. The potential of an electrode (or, for example, the transmission in the case of a phototitration) is recorded. as a function of the volume of titrant added. Titrant (also known as reagent) A solution of precisely know concentration with a titration is performed. Primary standard A substance having a high and well-defined degree of purity, with which a titrant is standardized. METTLER DL21/DL25 101Units Mole Abasicunitused for many concentration units. The amount of substance that contains 6.025 + 10° elementary entities (atoms, molecules, ions, electrons). Molar mass M (previously molecular weight) (Unit: g/mot) ‘The mass of one mole of a particular substance. For example: M (H,SO,) = 98.078 g/mol = 98.078 mg/mmol Equivalent (Equivalent number z*) ‘The equivalent indicates the number of reaction partners of a substance which participate in a specific reaction. For example: z (H,SO, as an acid) = 2 (H’, protons, hydrogen ions) Concentration c (Equivalent concentration) ‘The concentration of the reagent moieties which participate in the reaction is specified in mol/L (previously meal. or normality N), eg. ¢(NaOH) = 0.1 mov © ("yp H,SO,) = 0.1 mollL or (4.904 g H,SO/L) © ("ls KMnO,) = 0.1 mol/L is identical to © (KMnO,) = 0.02 mol/L (3.1608 g KMnO/L) The following relation applies: Equivalent concentration is equal to the amount-ot-substance concen- tration multiplied by the equivalent number c= ("le X)=2°C(X) 102 METTLER DL21/DL25If your DL21/25 conforms to IEC-348 (,IEC-348" on the model plate), the following data and descriptions apply: Notes and warnings for DL21/25 following IEC-348 This instrument of protection class 1 has been constructed and tested in accordance with IEC publication 348, Safety requirements for electronic measuring instruments, and has left the factory in perfect condition with regard to safety. To maintain this condition and ensure hazard- free operation, the user must comply with the notes and warnings in these operating instructions. The instrument is intended for indoor use. It can occasionally be exposed to temperatures between +50 °C and 10 °C with any adverse effect on its safety. Before the instrument is switched on, it must be ensured that the operating voltage set on the instrument matches the power supply voltage. If this instrument is operated via an autotranstormer from a power supply of higher voltage, it must be ensured that the base of the transformer is connected to the neutral conductor of the. power supply. The power plug may only be plugged into a grounding-type receptacle. The protective action must not be nullified by an extension cable without a protective conductor. When covers are opened or parts removed, except where this is possible by hand, live parts may be exposed. Points of connection may also be live. Before an adjustment, maintenance work, corrective maintenance or part replacement, the instrument must be disconnected from all voltage sources if it needs to be opened It must be ensured that only fuses of the specified type and specified rated amperage are used as spares. The use of repaired fuses or short-circuiting of the fuse holders strictly forbidden. Should it appear that hazard-free operation is no longer possible, the instrument must be disconnected from the power supply and secured against inadvertent operation. It must be assumed that hazard-free operation is no longer possible + when the instrument shows visible signs of damage, + when the instrument no longer operates, + after a lengthy period of storage under unfavorable conditions, + after subjection to severe transport stress. METTLER DL21/DL25 103Changing the operating voltage Technical data Power supply voltage: 100/117 V Optional equipment for 220/240 V for 100/117 V 220/240 V ‘The transformeris attached to the upper housing. Plug the cable connector (2) onto the spade connector marked with the local power-line voltage. When reassembling the instrument, make sure thatthe adjustmentwheel tor the stirrer speed (3) islined up with the slot provided for itin the upper housing. If the RS232C data output is installed, insert it by pressing it very lightly into the upper housing. Reinsert and tighten the seven screws (1). Pull out the fuse holder (arrow) between the ower switch and the power connector with a screwdriverand check the rating of the microfuse: 110/117 V, 800 mA, slow-blow, Order No. 20182 220/240 V, 400 mA, slow-blow, Order No.51367. (+10 %-15 %) Microfuses 400 mA, slow-blow, Microfuses 800 mA, slow-blow, Order No. Set of 3 51367 Set of 3 20182 data and descriptions in the preceding sections of these Operating Instructions apply! If, on the other hand, the model plate of your DL21/25 carries the designation ,EN-60950", all | 104 METTLER DL21/DL25‘The following applications are stored as methods 36...50 in the titrator DL25. They are optimized, but can easily ie eam be modified. They are documented in detail in the applications brochure DL25. No.| Compound sample CONST | indication | Titrant, CONC | Resuit 36 | Phosphoric acid Sm, 0.1 molt 200 |oati1sc |NaoH 0.1 | ~100 mmolt 37 | Phosphoric acid Sm, 0.1 mol 200 |DG111-8C ]NaOH 0.1 | ~100 mmolt. 38 | Al(OH), Ma78.00, 2-3 |Antacidum,0.1g) 26 |DGt11-Sc | HCI 01 | 203 mg/g 39 |CaCO,"Ma100.08, 226 |CaC0,-0.259 | 5.005 DG111-SC |HCINaOH 1.0 | 99.9 % 40 | Alcalinity Water, 50 ml. 20 |oatt1-s¢ | HC! o1 mmol. 41 | Epoxicic oxygen Epox resin-o.t) 0.1 [DG113-s0"|HoI0, 0.1 | 083 movr00g 42 | Acidic components Used, 1.39 | 66.1 | DG113-SC* | KOH o1 | -5 TAN 48 |K,C1,0,,M=294.14, 206 |Standard, 100% | 4.903 [DM140-SC | Mohr 0.1 | 99.85 % 44 | Na-Gyclamato, Ma Swestener,~0.1 g| 20.122 |DM140SC |NaNO, 0.1 | 99.99% 45 |H,0,,Ma34.014,262 |Solutin, tm | 17.007 | DM140-SC | KMn0, 0.1 | 7.7 ot 46 | SO, Ma64062, 2-2 |Wine, 50mt | 640.62 [OMI42 | lod ot | 26 mgt 47 |Ca,Mgashardness |Water, 200ml | 500.45 |DPSE0 | EDTA 0.1 | 165. ppm 48 |Ca,Mgashardnoss |Water, 50mL | 2001.8 |Hoi41 [EDTA 0.1 | 216 ppm 49 | Acctic acid, M=60.0 ——|Ketchup,1..29 | 6.005 |DGI11-sc |NaCH ot | 1.38 % 50 | Chloride as NaCIM-58.44| Ketchup, 1..2g| 5.844 |DM141-SC |AgNO, 0.1 | 268 % * DG113-SC replaces the DG1 12 electrode which was used in these applications List of corresponding configuration parameters and of CONST REAG No.) 1 2 3 45 6 7 8 9 A BC |C.REAG ° 1 1 05 | 10 0 o o 1 0 © 0 0 | 1.0000 3s | ss 1 05 | 12 0 10] 9823 101 0 5 18 0 | aos 37 joo 2 3 | 15 0 10| 4823 ti 0 5 18 0 | o2oa 38 | 7014 102 90 | 2 2 of] 43 1 0 0 6 0 | onan se] 1 2 3] 2 o to] 20 101 0 5 18 0 | ozos 40 [4 2 o| t0 o of] 80 1 0 o 0 0 | onan 41 | 1001 32 05 | 10 500 60 | 3011 101 210 5 0 15 | o2oa 42 | 3003 247 0 | 10 0 60 | 11 101 1810 8 18 0 | o2o4 43 | 2001 1111 05 | 10 200 10 | 211 tor 0 5 15 0 | 0049 44 | toot to2 05 | 10 300 180 | 201 tor 0 5 0 10) 04732 45 | 1001 1011 2] 10 100 0 | 600 1 0 5 10 10 1 as | 1005 31 0 | 2005 too 0 | 50 4 0 0 0 «0 | 00881 47 | 2001 2011 05 | 10 400 90 | 301 wor 1] 10 0 3 2 48 | 1 1104 02 5 0 10 | 301 tor 1 5 0 38 2 a] 1 2 0] 1 84 i] 21 101 0 5 15 0 | o2042 so; 1 1 02] 10 o 1 | 200 101 0 5 18 0 2 METTLER DL21/0L25, 105“Appendix: index Abort & Accessories 78 Acetic acid 98 Acid capacity 41, 42 Acid content 38 Acid mixture 13 ‘Acid number 60 Acoustical signal 29 D Air bubbles 11 Alkalinity, total 41 Aluminum 57 ‘Amalgamated silver electrode 57 ‘Anticipation 27 ‘ASTM D664 45 E ‘ASTM D664/D2806 43 ‘ASTM 02896 46 BACK 56 Back titration 47, 55, 57 Base number 43 Base capacity 41 Beep 29 Blank value 58 Blank value determination 59 Block key functions 9 Butter potentials 43 F BURETimL 11 Burette 9, 11, 89 H Burette volume 28 BUSY 13 1 Calculation constant 30 Calibration 35 CONC 10,32 Concentration 10, 32, 102 L Conditioning 66, 68 Configuration 20 Configuration data 108 M Configuration parameter 1. 22, 41, 45, 48 Configuration parameter 2 25, 45 Configuration parameter 3. 28, 48, Configuration parameter 4 28 Configuration parameter 5 28, 38 Configuration parameter 6 29 Configuration parameter 7 29 Configuration parameter 8 21 Configuration parameter 9 66, 68 Configuration parameter A 67 Configuration parameter B 48, 67 Configuration parameter C67 CONST 30 CONST REAG 32, 34 Control 25, 27 Data storage 23 Date 7 Derivative 15,29 Dispensing 12, 66, 67, 75 Dynamic control 25, 26 EDTA 57 Electrode parameters 95, 36 Electrodes 9 End point 28, 38, End point titration 23, 38 Equilibrium 25,26 Equivalence point 100 Equivalence point potential 14 Equivalent concentration 102 Error messages 95 Excess 55, 56 Fatty acids 60 Half neutralization value 14, 100 IDENT 13 Sample identification 13 Increments 25 Interface 72 LMS 24 Line recorder 94 Mains voltage 86 Master 73 Matrix printer 21, 76 Maverick 63 Maximum increment 25, 27 Maximum volume 28 Maximum determination 53 Mean value 63 Measurement 37 Measuring signal in mV 8 METTLER DL21/DL25Measuring signal inp 8 Measuring system 75 Method 17 Method printout 18 Method storage 76 Method, delete 19 Method, saving of 18 Methods list. 18 Minimum increment 25 Minimum determination 53 Negative trend 24 and mvalue 41 pH measurement 8 pHstat table 48 pH-stat titration 47 Phosphoric acid 39 Positive trend 24 Power on 7 Predispensing 28 Pretitration for pH stat 50 Reagent consumption 14 Reciprocal value 31 Relative standard deviation 64 Remote control 71 RESET 7 Resolution, high 24 Result calculation 30, 63 Result presentation 29 Result unit 31 Rinsing 66, 67 Rinsing unit 87 RS2320 72 Runaway 63 ‘Sample input 66 ‘Sample changer ST20A 61, 66, 70, 73, 97 ‘Segmented curve 54 SERIES INPUT 61 2 SERIES INPUT 63 9 SERIES INPUT 63 Series 61 Series sample data 65 Series titration 66 Set value 32 Signal vs time 29 Slave 73 Special caloulations 31 ST20A (ST20) 66 Standard compound 32 Standard Deviation 63, Start potential 14 Start signal 29 Statistical evaluation 63 Stier 8 Stirring time 29 Subsequent evaluation 14, memo card System configuration 21 Table of measured values 16 TANTBN 43 Threshold 25, 28 Time behaviour 25 Time condition 26 Time interval 26 Titer 10 Titrant addition 25 Titrant concentration 32 Titration 13 Titration curve 15, 29, 40, 101 Titration head 87 Titration modes 22, 75 Titration type 22 Trend 24 ‘Two end points 39 Voltage 86 WEIGHT 13 Weight input 13 METTLER DL21/DL25 107ppendix |: Configuration data +_] [Mone] Call configuration: 1st digit: parameter number 2nd to Sth: parameter value x] Cx] Cx) [x Enter parameter value with max. 4 digits RUN) RESET Reset to standby oe [eee SI atone Gy (ate Oe coe) -_—_—— uJ METTLER DL21/0L25To protect your METTLER TOLEDO product's future: METTLER TOLEDO Service assures the quality, measuring accuracy and preservation of value of all METTLER TOLEDO products for years to come. Please send for full details about our attractive terms of service. Thank you. Printed on 100% chlorine ee pape, er the sake of aur enironnent ‘Subject een! changes and othe avaltity oe acessories supplied wi he instunens *70s088" {© Netle-Toledo Gmbs 1992, 1983, 1994, 1996, 1998 ME-7O40940 pried inUSA. 9804/2.12 US Mettr-Toled, Inc, Mighstowa, NJ 08520-0071, Te, (609) 488 3000, Fox (609) 586-5481