Titration Excellence AGC Book 20% Cyan - ::: BK ...bikeitech.com/DATAS/es_free3/f_49780bd55e351.pdfAGC Book 20% Cyan 34 Application brochure Titrators T50 T70 T90 Selected METTLER

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34Application brochure

TitratorsT50T70T90

Selected METTLER TOLEDO Methods for Titration Excellence Line

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EDITORAL

Dear Reader

METTLER TOLEDO’s business area titration is proud to present the first selected application methods for the new Titration Excellence line. It consists of the three models T50, T70 and T90 and offers many advantages such as One Click Titration™, Plug & Play and Method database. The T50 represents the first level of excellence in titration and offers much more than a simple titrator: a terminal with brilliant touch screen, expandable with dispensing burette drives, comprehensive communication connections, and preconfigured system application packages. The all-rounder – the T70 – additionally shows further advantages. It allows the performance of manual operations, such as burette rinsing, while an analysis is running. An additional sensor card can be added and it can be upgraded to the highest model (T90). The T90 is the most powerful titrator: parallel titrations can be run while up to 6 different manual operations are running at the same time. It features unlimited flexibility and expansion possibilities in hardware and software.

No matter which model of the new line you choose – method development has never been easier thanks to the superb, intuitive and consistent graphical user interface using the color touch screen terminal. The 38 selected METTLER TOLEDO methods which are pre-programmed in the standard delivery of every model have been developed and extensively tested on real samples by the Market Support Group Analytical Chemistry. These methods are ready-to-use without modifications, or they can act as excellent starting points for method development.Furthermore, 13 application modes have been created in order to find the right control parameters efficiently. Depending on the indication and the chemistry taking place during titration, one or more application modes can be selected. Every application mode shows three sets of control parameters which you can select from (cautious, normal and fast), depending on the requirements for your specific titration.

This application brochure gives a short introduction into the method development possibilities of the Titration Excellence instruments, lists the parameters of all application modes in detail, shows the structures of all method templates and presents all METTLER TOLEDO methods including procedures, literature references and results.

We wish you much success titrating with the METTLER TOLEDO Titration Excellence line.

Mike Treyer Rolf Rohner Market Support Manager BA Titration Marketing Manager BA Titration

METTLER TOLEDO

CONTENT General Information I Introduction I METTLER TOLEDO Methods II Method Templates IV EQP Titration V

Application Modes V Learn Titrations VII

38 METTLER TOLEDO Methods Page 1 21 Method Templates Page 115 13 Application Modes Page 125 Figure 1: Excellence in titration: Titration Excellence Line

METTLER TOLEDO

I

GENERAL INFORMATION

Introduction No matter what analysis tasks you are challenged with - the process to meet specific analytical requirements begins with the analysis method. The Titration Excellence line featuring One Click TitrationTM is designed to be simple, efficient, modular and secure – not only in routine use but also in method development. The modular method concept allows customization of methods according to your specific needs. Methods are made up of method functions which in turn can be flexibly deleted, edited or inserted at almost every position within the method.

Figure 2: Inserting a method function in the desired place Not only single method functions can be inserted or deleted, it is possible to add or remove complete analysis loops at once – for more efficient method development. Figure 3: Removing a complete analysis loop by deleting the method function “Sample”

METTLER TOLEDO

II

Secure method development is achieved by assigning user rights which prevent methods from being changed or deleted by unauthorized personnel. In addition, every method can be protected by its author. A protected method can only be modified or removed by an administrator or the author him/herself. Figure 4: Protecting a method (method function “Title”) The following chapters show how simple it is to create methods for your specific purposes. The main features to achieve this are: • Pre-programmed METTLER TOLEDO Methods • Pre-programmed method templates • Pre-programmed application modes • Learn titration

METTLER TOLEDO Methods The METTLER TOLEDO method concept is well-known and has been established for many years. In the first version all Titration Excellence instruments feature 38 different, pre-programmed METTLER TOLEDO methods which represent a selection of the most important applications in the field of titration. One important advantage of these methods is that they are ready-to-use: you simply select one from the method list and start it. Even the resources such as titrants, sensors, substances etc. needed to execute the methods are already predefined. METTLER TOLEDO methods were optimized for the analysis of certain applications. Your specific application might require a slight adaptation of the method. Simply change the method as described before and save it under a different method ID.

METTLER TOLEDO

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Note: Method ID’s starting with an “M” followed by numbers are reserved for METTLER TOLEDO methods. Method ID Title PageM400 Acetic acid content in vinegar 1 M401 Ammonium chloride content 4 M402 Free fatty acid content 7 M403 Blank solvent FFA 10 M404 Chloride content in Ketchup 13 M405 Total hardness of tap water 16 M406 Ca + Mg content of tap water 19 M407 Sulfate content 22 M408 Barium content conductometric 25 M409 Copper content 28 M410 Hydrogen peroxide content 31 M411 Vitamin C content voltametric 34 M412 Vitamin C content amperometric 37 M413 SDS content photometric 40 M414 SDS content potentiometric 43 M415 m-Value of tap water (EP) 46 M416 p-Value of tap water (EP) 49 M417 Antacid (Stating) 52 M418 HCl content (EP) 55 M419 Free SO2 content in wine (EP) 58 M420 Water content KF (EP) 61 M421 Titer KF (EP) 64 M422 Drift KF (EP) 67 M423 Standby KF (EP) 70 M424 Bromine number ASTM D1159 (EP) 73 M425 Blank ASTM D1159 (EP) 76 M426 Acid number ASTM D664 79 M427 Blank ASTM D664 (EP) 82 M428 Base number ASTM D4739 85 M429 Blank ASTM D4739 88 M430 Base number ASTM D2896 91 M431 Blank ASTM D2896 94 M432 Chloride content in motor oil 97 M433 Mercaptan sulfur ASTM D3227 100 M434 SDS content (2-phase) 103 M435 Titer 0.1 mol/L NaOH 106 M436 Calibration DG111-SC 109 M437 HCl content conductometric 112

Table 1: METTLER TOLEDO methods

METTLER TOLEDO

IV

Method Templates Another simple and efficient way to obtain your specific method is to use a method template. Such templates define the structure of a method, namely the sequence of method functions. By pressing the “New” button in the method list which is accessible in the submenu Home>>Methods, a list of various method templates is displayed. Simply select the template that best fits the structure of your specific method and edit it according to your demands. Title Titrator Models Page EQP T50 / T70 / T90 115 EP T50 / T70 / T90 115 Stating T50 / T70 / T90 115 Measure T50 / T70 / T90 116 2-phase T50 / T70 / T90 116 Learn-EQP T50 / T70 / T90 116 Titer with EQP T50 / T70 / T90 117 Titer with EP T50 / T70 / T90 117 Calibration T50 / T70 / T90 117 Calibration segmented T50 / T70 / T90 118 Blank with EQP T50 / T70 / T90 118 Blank with EP T50 / T70 / T90 118 EP / EQP T50 / T70 / T90 119 EQP / EQP T50 / T70 / T90 119 EP / EP T50 / T70 / T90 120 Titer with EQP & EQP T70 / T90 120 Titer with EP & EP T70 / T90 121 Calibration & EQP T70 / T90 121 Calibration & EP T70 / T90 122 Calibration & Titer with EQP & EQP T70 / T90 123 Calibration & Titer with EP & EP T70 / T90 124

Table 2: Method templates Note: Multiple-loop methods (and method templates) require a T70 or a T90 titrator. A method loop characterizes the part of the method which every sample of a sample series runs through. It starts with a method function “Sample” and end with the method function “End of sample”. A multiple-loop method therefore is nothing else but a complex method made up of several methods. Most parameters of a selected method template show default values. After editing them, the method template has to be saved as a user method using an appropriate method ID before it can be started. These user methods which can also be developed from METTLER TOLEDO methods are added to the method list.

METTLER TOLEDO

V

EQP Titration The equivalent point (EQP) titration is the most frequently used analysis type in the field of titration. The control parameters of the method function “Titration (EQP)” determine whether the method is suitable for your application or not. The optimal control parameters for your EQP titration can efficiently be developed either using application modes or the intelligent Learn Titration.

Application Modes The parameters of the method subfunction “Control” define how a titrant is added and how the measurement points needed for evaluation are taken. Application modes are predefined sets of control parameters which are optimized for the chemical reaction involved in titration such as precipitation, complexation etc. Depending on the sensor type and measurement unit selected in the subfunction “Sensor”, one or more application modes are available in the subfunction “Control”. Note: all subfunctions mentioned here refer to method function “Titration (EQP)”.

Subfunction “Sensor” Subfunction “Control”

Sensor type Unit Application Modes Page pH pH mV

Acid / base Acid / base (non aq.)

125 125

mV mV Precipitation Precipitation (non aq.) Redox

126 126 126

mV ppm pX ISE

pM

Precipitation 127

mV %T Phototrode A

Precipitation Complexation

127 127

mV Redox 128 Polarized uA Redox 128 oC

oF Temperature K

Acid / base 129

mS uS mS/cm Conductivity

uS/cm

Acid / base Precipitation

129 129

Table 3: Application modes for different sensors and measurement units It is important to note that an application mode shows different control parameters for different sensors (e.g. “Acid / base” for a pH sensor does not contain the same parameters as “Acid / base” for a conductivity sensor).

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For every application mode there are 3 pre-programmed sets of parameters available. You select your optimal parameter set from the following options provided under the parameter “Control”: • Fast: Parameter set for fast titrations • Normal: Parameter set for the majority of titrations • Cautious: Parameter set for critical titrations Getting a good starting point on the way to optimal control parameters for your application is very simple: select “Fast”, “Normal” or “Cautious” and choose an application mode (if more than one is possible)! In case you would like to view the pre-programmed parameters, just click on the check box “Show parameters”. If you wish to change the selected control parameters, simply change the parameter “Control” to “User” (see figure 5). This doesn’t change the parameters but enables you to edit them.

Figure 5: Parameters of subfunction “Control” of method function “Titration (EQP)”

METTLER TOLEDO

VII

Learn Titration Let your Titration Excellence instrument learn the control parameters for optimal performance of your titration with the “Titration (LearnEQP)” method function. In this method function, no control parameters have to be selected – they are determined with the titration of the first sample. After the analysis, the “Titration (LearnEQP)” method function turns into a regular method function “Titration (EQP)”, showing the determined parameters. When running a series of samples, the parameters determined by sample 1 are applied to all subsequent samples. There is no need to create another method or to run another series. Note: The statistics calculation discards the result of the first sample. Titration Excellence Figure 6: Subfunctions of method function “Titration (Learn-EQP)”

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Figure 7: Terminal to control the Titration Excellence instruments T50 / T70 / T90

METTLER TOLEDO

METTLER TOLEDO METHODS

Content Method ID Title PageM400 Acetic acid content in vinegar 1 M401 Ammonium chloride content 4 M402 Free fatty acid content 7 M403 Blank solvent FFA 10 M404 Chloride content in Ketchup 13 M405 Total hardness of tap water 16 M406 Ca + Mg content of tap water 19 M407 Sulfate content 22 M408 Barium content conductometric 25 M409 Copper content 28 M410 Hydrogen peroxide content 31 M411 Vitamin C content voltametric 34 M412 Vitamin C content amperometric 37 M413 SDS content photometric 40 M414 SDS content potentiometric 43 M415 m-Value of tap water (EP) 46 M416 p-Value of tap water (EP) 49 M417 Antacid (Stating) 52 M418 HCl content (EP) 55 M419 Free SO2 content in wine (EP) 58 M420 Water content KF (EP) 61 M421 Titer KF (EP) 64 M422 Drift KF (EP) 67 M423 Standby KF (EP) 70 M424 Bromine number ASTM D1159 (EP) 73 M425 Blank ASTM D1159 (EP) 76 M426 Acid number ASTM D664 79 M427 Blank ASTM D664 (EP) 82 M428 Base number ASTM D4739 85 M429 Blank ASTM D4739 88 M430 Base number ASTM D2896 91 M431 Blank ASTM D2896 94 M432 Chloride content in motor oil 97 M433 Mercaptan sulfur ASTM D3227 100 M434 SDS content (2-phase) 103 M435 Titer 0.1 mol/L NaOH 106 M436 Calibration DG111-SC 109 M437 HCl content conductometric 112

M400

Acetic acid, CH3COOH,M = 60.05 g/mol, z = 1

50 mL deionized water

Sodium hydroxide, NaOHc(NaOH) = 0.1 mol/L

Titration Excellence T50/T70/T90Rondolino Sample Changer

CH3COOH + NaOH =CH3COONa + H2O

DV1010 buretteTitration beaker ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Neutralization before final disposal asaqueous solution.

Wastedisposal

Preparation and ProceduresVinegar, 0.7-1 g. Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG115-SCIndication

Acetic Acid Content in Vinegar

Note:This method allows a fully automated analysis procedure. Themethod can be easily modified for manual operation. Select"Manual stand" in the method function "Titration stand".

1) Adjustment of the DG115-SC pH glass electrode:The electrode is adjusted using pH buffers 4.01, 7.00, and9.21before starting the analysis.

2) The titer of sodium hydroxide is determined using potassiumhydrogenphthalate as a primary standard (KHP): 80 mg aredissolved into 50 ml deion. water and titrated.

3) Approximately 1 g vinegar is added to 50 mL deionizedwater into a titration beaker.

4) In this application, the sample series was analysed using aRondolino sample changer in combination with a diaphragmpump. The rinsing time was defined to 2 s. In this way, theelectrode is cleaned with deionised water before starting thesubsequent sample.

1) The method parameters have been developed and optimisedfor the above mentioned sample. Since there are different kindsof vinegar, it may be necessary to slightly adapt the method toyour specific sample.

Remarks

R1: Content (%), expressed as w/w

R1 = Q*C/m,C = M/(10*z)

Calculation

The acetic acid content is determined in vinegar by titration with sodium hydroxide.

Standard Potassium hydrogen phthalate, 80 mg

Thomas HitzAuthor

1

Table of measured values

All results Method-ID M400 Sample Vinegar (1/1) R1 (Content) 4.713 % Sample Vinegar (1/2) R1 (Content) 4.734 % Sample Vinegar (1/3) R1 (Content) 4.718 % Sample Vinegar (1/4) R1 (Content) 4.717 % Sample Vinegar (1/5) R1 (Content) 4.722 % Sample Vinegar (1/6) R1 (Content) 4.724 %

Statistics Method-ID M400 R1 Content Samples 6 Mean 4.738 % s 0.007 % srel 0.152 %

Titration curve

Results

2

Method M400 Acetic acid content 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M400 Title Acetic acid content invinegar Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Vinegar Entry type Weight Lower limit 0.7 g Upper limit 1.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary

003 Titration stand (Rondolino TTL) Type Rondolino TTL Titration stand Rondolino TTL 1

004 Stir Speed 35% Duration 10 s Condition No

005 Titration (EQP) [1]Titrant Titrant NaOH Concentration 0.1 mol/LSensor Type pH Sensor DG115-SC Unit pHTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode Volume Potential 1 ml Wait time 5 sControl Control User Titrant addition Dynamic dE(set value) 12 mV dV(min) 0.002 mL dV(max) 0.5 mL Meas. val. acquisition Equilibrium controlled dE 0.5 mV dt 1 s t(min) 3 s t(max) 30 sEvaluation and Recognition Procedure Standard Threshold 5 pH/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method006 Calculation R1 Result Content Result unit % Formula R1=Q*C/m Constant C=M/(10*z) M M[Acetic acid] z z[Acetic acid] Decimal places 3 Result limits No Add. statistics functionalities No

007 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V Last titration function log dE/dV - V No d2E/dV2 - V No E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

008 End of sample

3

M401

Ammonium chloride, NH4Cl,M = 53.49 g/mol, z = 1



Titration Excellence T50/T70/T90

NH4Cl + NaOH = NH4OH + NaCl


METTLER TOLEDO


Wastedisposal

Preparation and ProceduresAmmonium chloride solution,5 mL 0.1 M NH4Cl solution

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG111-SCIndication

Ammonium Chloride Content in Aqueous Solution

1) The titer of sodium hydroxide is determined using potassiumhydrogenphthalate as a primary standard (KHP): 80 mg aredissolved into 50 ml deion. water and titrated.

2) 5 mL of 0.1 M ammonium chloride solution are added in thesample beaker. Its concentration is stored as auxiliary valueH[NH4Cl] in g/mL.

3) Dilute the sample with 50 mL deionised water and start thetitration method.

4) The content is expressed as % w/w. Since a standardaqueous solution of ammonium chloride was used, the result inthe calculation function indicates the recovery rate ofammonium chloride in solution.

1) The method parameters have been developed and optimisedfor the above mentioned sample. If the composition of yoursample is different, it may be necessary to slightly adapt themethod parameters to your specific sample.

2) The method can be easily modified for automated operation.Select the appropriate sample changer in the method function"Titration stand".

Remarks


R1 = Q*C/m,C = M/(10*z)

Calculation

Determination of the weak acid ammonium chloride in aqueous solution by titration with sodium hydroxide.


Maria-José SchmidAuthor

4


All results Method-ID M401 Sample Ammonium chloride solution (1/1) R1 (Content) 101.193 % Sample Ammonium chloride solution (1/2) R1 (Content) 101.345 % Sample Ammonium chloride solution (1/3) R1 (Content) 101.466 % Sample Ammonium chloride solution (1/4) R1 (Content) 101.156 % Sample Ammonium chloride solution (1/5) R1 (Content) 101.305 % Sample Ammonium chloride solution (1/6) R1 (Content) 101.117 %


Titration curve

Results

5

Method M401 Ammonium chloride content 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M401 Title Ammonium chloride content Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Ammonium chloride solution Entry type Fixed volume Volume 5 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C

003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1

004 Stir Speed 30% Duration 10 s

005 Titration (EQP) [1]Titrant Titrant NaOH Concentration 0.1 mol/LSensor Type pH Sensor DG111-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 30%Predispense Mode Potential Potential - 120 mV Wait time 10 sControl Control User Titrant addition Dynamic dE(set value) 8 mV dV(min) 0.02 mL dV(max) 0.2 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 1.0 s t(min) 3.0 s t(max) 30.0 sEvaluation and Recognition Procedure Standard Threshold 20 mV/mL Tendency Negative Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential Yes Potential -300 mV At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method006 Calculation R1 Result Content Result unit % Formula R1=Q*C/(m*H[NH4Cl]) Constant C=M/10*z M M[Ammonium chloride] z z[Ammonium chloride] Decimal places 3 Result limits No Add. statistics functionalities No


008 End of sample

6

M402

Free fatty acids as mg KOH/g sample,M=56.1 g/mol, z=1

60 mL ethanol:diethylether 1:1 (v/v)

Potassium hydroxide in ethanol, KOHc(KOH) = 0.02 mol/L

Titration Excellence T50/T70/T90Rondolino Sample Changer1 additional dosing unit

R-COOH + KOH = R-COO- + K+ + H2O

R-COOH: Free fatty acids

DV1010 and DV1020 glass burettesTitration beaker ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Dispose as organic solventWastedisposal

Preparation and ProceduresOlive oil, 2-4 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Free Fatty Acids Content in Edible Oil

Note:This method allows a fully automated procedure using asample changer and an additional dosing unit. The method canbe easily modified for manual operation. Select "Manual stand"in the method function "Titration stand".

1) The titer is determined using benzoic acid: 25 mg are addedinto a glass titration beaker. They are dissolved with it with 60mL solvent mixture. Since the sample amount is rather small, abalance having a resolution of at least 0.1 mg is needed.CAUTION: Benzoic acid is an aggressive substance. Avoidcontact with skin and eyes, particularly.

2) A blank value is determined for every new batch of solventmixture (see M403) and stored as B[Solvent FFA].

3) Approx. 2-4 g of olive oil is weighed into a titration beaker.

4) 60 mL solvent mixture are added by an additional dosingunit (20 mL burette) in two steps to improve sampledissolution. It can be performed manually with a pipette.

5) After each titration the DG113-SC sensor was rinsed withsolvent by means of the diaphragm pump of the Rondolinosample changer (Settings: Pos. "1").

1) The method parameters have been optimised for the sampleused in this application. Thus, it may be necessary to slightlyadapt the method to your specific sample.

2) The free fatty acid content (FFA) is defined as the amount in gof oleic acid (C18H34O2) in 100 g sample. Depending on the typeof oil, it is also indicated as the amount of lauric or palmitic acid

3) The acid number is a measure of the decomposition bylipase enzyme in edible oil and fats. The decomposition isspeeded up by heat and light. Rancidity is due to decompositionand it is accompanied by free fatty acid formation.

4) To ensure hydration of the DG113 glass membrane, theelelctrode is stored over night in water. Before titration, wash theelectrode with solvent mixture.

5) Some samples can give rather flat titration curve, and noisecan appear. To increase the potential jump, 1 mL 0.05 mol/Lbenzoic acid is added to 1 L of solvent mixture. This si also ofhelp if the blank determination is not possible due to very lowtitrant consumption.

Literature:- METTLER TOLEDO Appl. brochure 24, ME-51 725 054.

Remarks

Acid number (mg KOH/g)R1=(Q-B[FFA])*C/m,C=M, z=1FFA in olive oil (g FFA/100g)R2=(Q-B[FFA])*C/m,C=M*0.1, z=1M[Oleic acid], z[Oleic acid]=1

Calculation

Determination of the free fatty acids (FFA) content in edible oil by potentiometric titration with ethanolicpotassium hydroxide in a non-aqueous mixture consisting of ethanol and diethylether (1:1 v/v).


Melanie NijmanAuthor

7


All results Method-ID M402 Sample Edible oil (1/1) R1 (Content) 0.846807 mg KOH/g R2 (Content) 0.426301 g/100g Sample Edible oil (1/2) R1 (Content) 0.845652 mg KOH/g R2 (Content) 0.425720 g/100g Sample Edible oil (1/3) R1 (Content) 0.847853 mg KOH/g R2 (Content) 0.426828 g/100g Sample Edible oil (1/4) R1 (Content) 0.847045 mg KOH/g R2 (Content) 0.426421 g/100g Sample Edible oil (1/5) R1 (Content) 0.847805 mg KOH/g R2 (Content) 0.426804 g/100g Sample Edible oil (1/6) R1 (Content) 0.842935 mg KOH/g R2 (Content) 0.424352 g/100g

Statistics Method-ID M402 R1 Content Samples 6 Mean 0.846350 mg KOH/g s 0.001856 mg KOH/g srel 0.219 % R2 Oleic acid content Samples 6 Mean 0.426071 g/100g s 0.000934 g/100g srel 0.219 %

Titration curve

Results

8

Method M402 Free fatty acid content 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M402 Title Free fatty acid content Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Edible oil Entry type Weight Lower limit 0.0 g Upper limit 5.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary


004 Dispense (normal)[1] Titrant Solvent FFA Concentration 1 Volume 20.0 mL Dosing rate 60.0 mL/min Condition No

005 Stir Speed 35 % Duration 10 s Condition No

006 Dispense (normal)[2] Titrant Solvent FFA Concentration 1 Volume 40.0 mL Dosing rate 60.0 mL/min Condition No

007 Stir Speed 35 % Duration 10 s Condition No

008 Titration (EQP) [1]Titrant Titrant KOH in EtOH Concentration 0.02 mol/LSensor Type pH Sensor DG113-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35 %Predispense Mode Volume Volume 1.0 mL Wait time 0 sControl Control User Titrant addition Dynamic dE(set value) 12.0 mV dV(min) 0.01 mL dV(max) 0.3 mL Meas. value acquisition Equilibrium controlled dE 1.0 mV dt 2 s t(min) 2 s t(max) 15 sEvaluation and recognition Procedure Standard Threshold 200 mV/mL Tendency Negative Ranges 0 Add. EQP criteria No

MethodTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

009 Calculation R1 Result Content Result unit mg KOH/g Formula R1=(Q-B[Solvent FFA])*C/m Constant C=M/z M M[Potassium hydroxide] z z[Potassium hydroxide] Decimal places 6 Result limits No Add. statistics functionalities No

010 Calculation R2 Result Oleic acid content Result unit g/100g Formula R2=(Q-B[Solvent FFA])*C/m Constant C=M/(10*z) M M[Oleic oil] z z[Oleic oil] Decimal places 6 Result limits No Add. statistics functionalities No


012 End of sample

9

M403

Acid components , z=1

--

Potassium hydroxide in ethanol, KOHc(KOH) = 0.02 mol/L


R-COOH + KOH = R-COO- + K+ + H2O

R-COOH: Free fatty acids

DV1010 and DV1020 glass burettesTitration beaker ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Dispose as organic solventWastedisposal

Preparation and Procedures60 mL ethanol:diethylether 1:1 (v/v)Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Blank Value of Free Fatty Acids (FFA) Solvent

Note:This method allows a fully automated procedure using asample changer and an additional dosing unit. The method canbe easily modified for manual operation. Select "Manual stand"in the method function "Titration stand".

1) The titer is determined using benzoic acid: 25 mg are addedinto a glass titration beaker. They are dissolved with it with 60mL solvent mixture. Since the sample amount is rather small, abalance having a resolution of at least 0.1 mg is needed.CAUTION: Benzoic acid is an aggressive substance. Avoidcontact with skin and eyes, particularly.

2) A blank value is determined for every new batch of solventmixture and stored as B[Solvent FFA].

3) 60 mL solvent mixture are added by an additional dosingunit (20 mL burette). It can be performed manually with apipette.

4) After each titration the DG113-SC sensor was rinsed withsolvent by means of the diaphragm pump of the Rondolinosample changer (Settings: Pos. "1").


2) To ensure hydration of the DG113 glass membrane, theelelctrode is stored over nigth in water. Before titration, wash theelectrode with solvent mixture.

3) If needed, the solvent is spiked with 1 mL 0.05 mol/L addedto 1 L of solvent mixture. In this way, the potential jump is morepronounced.


Remarks

Blank valueR1=Q , mmol

Calculation

Determination of the blank value for free fatty acids (FFA) content in edible oil by potentiometric titration withethanolic potassium hydroxide in a non-aqueous mixture consisting of ethanol and diethylether (1:1 v/v).



10


All results Method-ID M403 Sample Solvent FFA (1/1) R1 (Consumption) 0.002486 mmol Sample Solvent FFA (1/2) R1 (Consumption) 0.002612 mmol Sample Solvent FFA (1/3) R1 (Consumption) 0.002697 mmol Sample Solvent FFA (1/4) R1 (Consumption) 0.002573 mmol Sample Solvent FFA (1/5) R1 (Consumption) 0.002638 mmol Sample Solvent FFA (1/6) R1 (Consumption) 0.002597 mmol Sample Solvent FFA (1/7) R1 (Consumption) 0.002543 mmol

Statistics Method-ID M403 R1 Consumption Samples 7 Mean 0.002592 mmol s 0.000068 mmol srel 2.615 %

Titration curve

Results

11

Method M403 Blank solvent FFA 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M403 Title Blank solvent FFA Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Solvent FFA Entry type Fixed volume Volume 60 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C 003 Titration stand (Rondolino TTL) Type Rondolino TTL Titration stand Rondolino TTL 1

004 Dispense (normal)[1] Titrant Solvent FFA Concentration 1 Volume 60.0 mL Dosing rate 60.0 mL/min Condition No005 Stir Speed 35 % Duration 60 s Condition No

006 Titration (EQP) [1]Titrant Titrant KOH in EtOH Concentration 0.02 mol/LSensor Type pH Sensor DG113-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35 %Predispense Mode None Wait time 0 sControl Control User Titrant addition Dynamic dE(set value) 8.0 mV dV(min) 0.005 mL dV(max) 0.03 mL Meas. value acquisition Equilibrium controlled dE 1.0 mV dt 1 s t(min) 3 s t(max) 30 sEvaluation and recognition Procedure Standard Threshold 200 mV/mL Tendency Negative Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method007 Calculation R1 Result Consumption Result unit mmol Formula R=Q Constant C=1 M M[None] z z[None] Decimal places 6 Result limits No Add. statistics functionalities No


009 End of sample

010 Blank Name Solvent FFA Value B=Mean[R1] Units mmol Limits No

011 Calculation R2 Result Blank Solvent FFA Result unit mmol Formula R2=Mean[R1] Constant C=1 M M[None] z z[None] Decimal places 6 Result limits No Add. statistics functionalities No

012 Record Results Yes Raw results No Resource data No Calibration curve No Method No Series data No

12

M404

Sodium chloride, NaCl,M = 58.44 g/mol, z = 1

50 mL sulphuric acid, H2SO4

c(H2SO4) = 0.02 mol/L

Silver nitrate, AgNO3

c(AgNO3) = 0.1 mol/L


NaCl + AgNO3 = AgCl + NaNO3


METTLER TOLEDO

Filtration. The precipitate (AgCl) has tobe classified as special waste. Theliquid phase has to be neutralized to pH7 before final disposal.

Wastedisposal

Preparation and ProceduresKetchup, 1.4-1.6 g Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM141-SCIndication

Chloride Content in Ketchup

1) The titer determination of silver nitrate is performed usingsodium chloride (NaCl) as a primary standard. Since smallamounts of salt cannot be weighed in exactly, it isrecommended to prepare an aqueous solution of NaCl, and thento add the standard with a pipette.

2) Approximately 1.5 g ketchup are added in a titration beaker.Ketchup is dissolved by adding 50 mL 0.02 mol/L H2SO4 .

3) After each sample the DM141-SC electrode, the stirrer andthe titraton dispensing tube are cleaned using a paper tissuesoaked with deionised water to completely remove any AgClresidue.

1) The method parameters have been developed and optimisedfor the above mentioned sample. Since there are differentketchup producers, it may be necessary to slightly adapt themethod to your specific sample.


Remarks


R1 = Q*C/m,C = M/(10*z)

Calculation

The chloride content in ketchup is determined by precipitation titration with silver nitrate. The content isexpressed as sodium chloride, NaCl (salt).

Standard NaCl, c(NaCl)=0.1 mol/L , 5 mL

Thomas HitzAuthor

13


All results Method-ID M404 Sample Ketchup (1/1) R1 (Content) 3.287 % Sample Ketchup (1/2) R1 (Content) 3.274 % Sample Ketchup (1/3) R1 (Content) 3.287 % Sample Ketchup (1/4) R1 (Content) 3.290 % Sample Ketchup (1/5) R1 (Content) 3.273 % Sample Ketchup (1/6) R1 (Content) 3.284 %


Titration curve

Results

14

Method M404 Chloride in ketchup 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M404 Title Chloride content in ketchup Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect SOP None

002 Sample Number of IDs 1 ID 1 Ketchup Entry type Weight Lower limit 1.4 g Upper limit 1.6 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary



005 Titration (EQP) [1]Titrant Titrant AgNO3

Concentration 0.1 mol/LSensor Type mV Sensor DM141-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode Volume Potential 1 ml Wait time 5 sControl Control User Titrant addition Dynamic dE(set value) 9 mV dV(min) 0.008 mL dV(max) 0.4 mL Meas. val. acquisition Equilibrium controlled dE 0.5 mV dt 1.0 s t(min) 3.0 s t(max) 30.0 sEvaluation and Recognition Procedure Standard Threshold 250 mV/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method006 Calculation R1 Result Content Result unit % Formula R1=Q*C/m Constant C=M/(10*z) M M[Sodium chloride] z z[Sodium chloride] Decimal places 3 Result limits No Add. statistics functionalities No


008 End of sample

15

M405

Magnesium and calcium as CaCO3,M = 100.09 g/mol, z = 1

10 mL 5% NH3-solution1 mL 0.1% Eriochrome Black T

EDTA, c(EDTA) = 0.1 mol/L

Titration Excellence T50/T70/T902 additional dosing units

Ca2+ + EDTA-H22- = Ca_EDTA2- + 2H+

Mg2+ + EDTA-H22- = Mg_EDTA2- + 2H+

3 DV1010 glass burettesTitration beaker ME-101974Olivetti Printer JobJet 210

METTLER TOLEDO

Neutralization with hydrochloric acidbefore final disposal.

Wastedisposal

Preparation and ProceduresTap or surface water, 50 mL Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DP5 PhototrodeTM, 660 nmIndication

Total Hardness of Tap Water by Photometric Titration

1) The titer determination is first performed using 0.1 mol/L zincsulfate (ZnSO4) standard solution: 5 mL ZnSO4 are added into atitration beaker and diluted with 50 mL deion. water.

2) 50 mL tap water are added into a beaker with a pipette.

3) 1 mL 0.1% Eriochrome Black T ethanolic solution is addedto the sample beaker.

4) The pH of the sample solution is adjusted by adding 10 mL5% NH3-solution. Important: Add ammonia solutionimmediately before titration and after the ErioT indicator solution.Note: Instead of ammonia solution it is possible to use boratebuffer pH10. Preparation: Dissolve 40 g sodium hydroxide(NaOH) in 500 mL water (Caution: solution gets hot!), add 65g boric acid (H3BO3) and fill up to 1000 mL with deion. water.

4) This method allows a fully automated analysis procedure byusing two additional burette drives. Nevertheless, the methodcan be modified for the manual addition of required reagents.

5) Before starting the subsequent sample, electrode and stirrerare cleaned and dried with a soft tissue.

1) After turning on the phototrode, wait for 15-10 minutes beforestarting analysis to achieve a stable light intensity.

2) Subsequently, first check the transmission signal of thephototrode in deionised water and set it to 1000 mV by turningthe knob on the top of it.

3) Avoid the formation of air bubbles during titration since theydisturb the photometric indication. Thus, select the appropriatestirring speed.

4) The wavelength can be also set to 555 nm instead of 660nm. In this case, the method parameter "Tendency" has to beset to "Positive".

5) The method parameters have been developed and optimisedfor the tap water samples used in this application. It may benecessary to slightly adapt the method to your specific sample.


Remarks

R1: Content (ppm)

R1 = Q*C/m,C = M*1000/z

Calculation

The total hardness of water, expressed as CaCO3 content of water is determined by complexometric titrationof calcium and magnesium at pH 10 using EDTA. The color change of the Erio T indicator (violet to blue) atthe equivalence point is sensed by a DP5 PhototrodeTM.

Standard ZnSO4 , c(ZnSO4)=0.1 mol/L, 5 mL


16


All results Method-ID M405 Sample Tap water (1/1) R1 (Content) 144.574 ppm Sample Tap water (1/2) R1 (Content) 144.462 ppm Sample Tap water (1/3) R1 (Content) 144.356 ppm Sample Tap water (1/4) R1 (Content) 144.216 ppm Sample Tap water (1/5) R1 (Content) 144.368 ppm Sample Tap water (1/6) R1 (Content) 144.550 ppm

Statistics Method-ID M405 R1 Content Samples 6 Mean 144.421 ppm s 0.135 ppm srel 0.093 %

Titration curve

Results

17

Method M405 Chloride in ketchup 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M405 Title Total hardness of tap water Author METTLER TOLEDO Date/Time 02.08.2006 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Water Entry type Fixed volume Volume 50.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C


004 Dispense Titrant ErioT Concentration 0.1 mol/L Volume 1.0 mL Dosing rate 60.0 mL/min


006 Dispense Titrant 5% NH3

Concentration 0.1 mol/L Volume 10.0 ml Dosing rate 60.0 mL/min


008 Titration (EQP) [1]Titrant Titrant EDTA Concentration 0.1 mol/LSensor Type Phototrode Sensor DP5 Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode Volume Volume 0.5 ml Wait time 5 sControl Control User Titrant addition Incremental dV 0.01 mL Meas. val. acquisition Equilibrium controlled dE 2.0 mV dt 1.0 s t(min) 3.0 s t(max) 20.0 sEvaluation and Recognition Procedure Standard Threshold 1000 mV/mL Tendency Negative Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method009 Calculation R1 Result Content Result unit ppm Formula R1=Q*C/m Constant C=M*1000/z M M[Calcium carbonate] z z[Calcium carbonate] Decimal places 3 Result limits No Add. statistics functionalities No

010 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V Last titration function log dE/dV - V No d2E/dV2 - V No E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No Condition No

011 End of sample

18

M406

Ca2+ , M = 40.08 g/mol , z=1Mg2+ , M = 24.31 g/mol , z=1

6 mL buffer pH 8.5 Acac/THAM:0.1 mol/L Acetylacetone and 0.2 mol/L THAM(Tris(hydroxymethyl)-aminomethane)

Na2-H2EDTA,c(EDTA)=0.1 mol/L


Ca2+ + H2EDTA2- = Ca-EDTA2- + 2H+

Mg(acac)2 + H2EDTA2-=Mg-EDTA2- + 2 AcAc- + 2 H+

acac: acetylcetone

2 DV1010 glass burettesTitration beakers ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Dispose as aqueous solution.Wastedisposal

Preparation and Procedures80 mL tap water Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DX240 Ca-ISE, DX200 Ref. electrode(DX200: Bridge electr. 3 mol/L KCl)

Indication

Calcium and Magnesium Content of Tap Water

Note: This method allows a fully automated procedure with anadditional dosing unit and a sample changer. The method canbe easily modified for manual operation. Select "Manual stand"in the method function "Titration stand".

1) The DX240 Ca-ISE and the reference electrodes are installed.2) A titer determination is run using 5 mL 50 ppm calciumcarbonate solution as a standard.3) Sample titration: Add 80 mL tap water into the titration beaker4) 6 mL pH buffer 8.5 Acac/THAM are added to the sample.This step has been performed using an additional dosing unit. Itcan be performed manually using a pipette.5) The sample is titrated with EDTA.

Automation:A Rondolino sample changer with a diaphragm pump wasused. The conditioning time was set to 30 s while the rinsingtime was defined to 2 s (Rondolino settings: 7).

Buffer pH 8.524.228 g THAM (0.20 mol) are added into a 1 L volumetricflask together with 10.01 g acetylacetone (0.1 mol/L). Deion.water is added for dissolution and to fill up to 1000 mL.

1) The method parameters have been optimised for the abovementioned sample. It may be necessary to slightly adapt themethod to your specific sample.

2) The DX240 Ca-ISE is sensitive to both Ca and Mg ions. Thecurve has two equivalence points. The titrant consumption up tothe first equivalence point yields the Ca-content. The additionaltitrant volume to the second EQP yields the Mg content.

3) In alkalinic buffered solutions Ca and Mg ions can be titratedsequentially provided that the complex formation constants havea ratio of 103-104. With EDTA, the ratio of the constants is about100. By adding an auxiliary complexing agent such as Acacwhich weakly complexes the Mg but not the Ca ion, the ratio ofthe constants can be adjusted.The concentration of acetylacetone significantly influences thesize of the equivalence point jumps. A high concentration ofacetylacetone increases the size of the calcium jump, therebymasking the magnesium jump. A low concentration will havethe opposite effect.

4) For titer determinations, make sure the pH of the sample afteraddition of the Acac/THAM buffer is 8.5. If it is not, an endpointtitration to pH 8.5 should be performed prior to the EQP titration.

Remarks

1) Ca content, ppmR1=Q*C/m, C=M*1000/zM=M[Calcium], z[Calcium]=12) Mg content, ppmR2=Q2*C2/m, C=M*1000/zM=M[Magnesium], z[Magnesium]=1

Calculation

Method for the determination of calcium and magnesium content of tap water by complexometric titrationwith EDTA. The titration is monitored using a calcium selective electrode.

Standard Calcium carbonate sol., 50 ppm

Madeleine BiberAuthor

19


All results Method-ID M406 Sample Tap water (1/1) R1 (Ca Content) 51.443 ppm Ca 2+

R2 (Mg Content) 4.359 ppm Mg 2+

Sample Tap water (1/2) R1 (Ca Content) 51.009 ppm Ca 2+












Statistics Method-ID M406 R1 Ca Content Samples 7 Mean 51.127 ppm Ca 2+

s 0.163 ppm Ca 2+

srel 0.318 % R2 Mg Content Samples 7 Mean 4.459 ppm Mg 2+

s 0.063 ppm Mg 2+

srel 1.417 %

Titration curve

Results

20

Method M406 Ca and Mg content of tap water 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M406 Title Ca and Mg content of tap water Author METTLER TOLEDO Date/Time 02.08.2006 15:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Tap Water Entry type Fixed volume Volume 80 mL Density 1 g/mL Correction factor 1.0 Temperature 25.0°C


004 Dispense (normal) [1] Titrant Buffer pH 8.5 Concentration 1 mol/L Volume 6 mL Dosing rate 60.0 mL/min

005 Stir Speed 50 % Duration 60 s

006 Titration (EQP) [1]Titrant Titrant EDTA Concentration 0.1 mol/LSensor Type ISE Sensor DX240-Ca2+

Unit mVTemperature acquisition Temperature acquisition NoStir Speed 50%Predispense Mode None Wait time 0 sControl Control User Titrant addition Dynamic dE(set value) 8.0 dV(min) 0.005 mL dV(max) 0.02 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 1 s t(min) 5 s t(max) 30 sEvaluation and Recognition Procedure Standard Threshold 100 mV/mL Tendency Negative Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 2 Combined termination criteria No

Method007 Calculation R1 Result Ca Content Result unit ppm Ca2+

Formula R1=Q*C/m Constant C=M*1000/z M M[Calcium] z z[Calcium] Decimal places 3 Result limits No Add. statistics functionalities No

008 Calculation R2 Result Mg Content Result unit ppm Mg2+

Formula R2=Q2*C/m Constant C=M*1000/z M M[Magnesium] z z[Magnesium] Decimal places 3 Result limits No Add. statistics functionalities No


010 End of sample

21

M407

Sulfate, SO42-

M=96.06 g/mol, z=1

2 mL Lithium acetate buffer8 mL 2-propanol

Barium chloride, BaCl2c(BaCl2) = 0.1 mol/L

Titration Excellence T50/T70/T902 additional dosing unitsRondo 60 Sample Changer

Ba2+ + SO42- = BaSO4

2 additional burettes DV1010Titration beakers ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Dispose as heavy metals containingaqueous solution.

Wastedisposal

Preparation and Procedures50 mL mineral water Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DX337-Ba ISE, DX200 Ref. electrode(DX200: Bridge electr. 3 mol/L KCl)

Indication

Sulfate Content of Mineral Water

Note: This method allows a fully automated procedure withadditional dosing units and a sample changer. The method canbe easily modified for manual operation. Select "Manual stand"in the method function "Titration stand".

1) Install the DX337-Ba ISE and the reference electrode.2) Perform a titer determination using 5 mL 0.1 mol/Lammonium sulfate standard solution.3) Sample titration: Add 50 mL tap water into the titration beaker4) Add 8 mL 2-propanol. This step has been performed with anadditional dosing unit. It can be done manually using a pipette.5) Add 2 mL lithium acetate buffer. This was performed with anadditional dosing unit. It can be done manually using a pipette.6) The sample is titrated with 0.1 mol/L BaCl2 solution.7) The electrode is conditioned in deionized water during 60 s.

Automation:A Rondo 60 sample changer was used. The conditioning timewas set to 60 s.


2) Ba(II)-ISE:- Fill the Ba-ISE and the electrode tip with the electrolyte.- Screw the electrode tip onto the shaft.- Shake the Ba-ISE 2-3 times to avoid the presence of airbubbles into the electrode tip. Rinse it with deion. water.- Condition it in 0.01 mol/L Ba-solution for 20-30 minutes.

3) For optimum precipitation of BaSO4 it is necessary to adjustthe pH with lithium acetate buffer.

4) Lithium acetate buffer solution:10.2 g lithium acetate dihydrate are dissolved in 500 mL deion.water in a beaker. Add 5.7 mL glacial acetic acid while stirring.Transfer to a 1 L volumetric flask and fill up to the mark withwater.

Literature:- METTLER TOLEDO Appl. brochure 33, ME-51 725 065.- METTLER TOLEDO Appl. brochure 19, ME-51 725 013

Remarks

Content, mg/L:

R1=Q*C/m,C=M*1000/z

M=M[Sulfate] , z=z[Sulfate]

Calculation

The sulfate content in mineral water is determined by precipitation titration with barium chloride as a titrant.The titration is monitored potentiometrically using a DX337-Ba2+ barium selective electrode.

Standard Ammonium sulfate sol., 0.1 mol/L

Cosimo De CaroAuthor

22


All results Method-ID M407 Sample Mineral water (1/1) R1 (Content) 882.82 mg/L Sample Mineral water (1/2) R1 (Content) 884.34 mg/L Sample Mineral water (1/3) R1 (Content) 883.12 mg/L Sample Mineral water (1/4) R1 (Content) 884.37 mg/L Sample Mineral water (1/5) R1 (Content) 886.92 mg/L Sample Mineral water (1/6) R1 (Content) 886.52 mg/L Sample Mineral water (1/7) R1 (Content) 883.78 mg/L

Statistics Method-ID M407 R1 Content Samples 7 Mean 884.55 mg/L s 1.59 mg/L srel 0.180 %

Titration curve

Results

23

Method M407 Sulfate content 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M407 Title Sulfate content Author METTLER TOLEDO Date/Time 02.08.2006 15:00 Modified -- Modified by -- Protect SOP None

002 Sample Number of IDs 1 ID 1 Mineral water Entry type Fixed volume Volume 50 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C

003 Titration stand (Rondo60/Tower A) Type Rondo60/TowerA Titration stand Rondo60/1A

004 Dispense (Normal) Titrant 2-Propanol Concentration 1 mol/L Volume 8 mL Dosing rate 60.0 mL/min

005 Dispense (Normal) Titrant Li-Acetate buffer Concentration 1 mol/L Volume 2 mL Dosing rate 60.0 mL/min


007 Titration (EQP) [1]Titrant Titrant BaCl2

Concentration 0.1 mol/LSensor Type ISE Sensor DX337-Ba2+

Unit mVTemperature acquisition Temperature acquisition NoStir Speed 30%Predispense Mode Volume Volume 3 mL Wait time 60 sControl Control User Titrant addition Incremental dV 0.1 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 2 s t(min) 10 s t(max) 45 sEvaluation and Recognition Procedure Asymmetric Threshold 30 mV/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method008 Calculation R1 Result Content Result unit mg/L Formula R1=Q*C/m Constant C=M*1000/z M M[Sulfate] z z[Sulfate] Decimal places 2 Result limits No Add. statistics functionalities No

009 Conditioning Type Fix Interval 1 Position Condition beaker Time [s] 60 Speed [%] 30


011 End of sample

012 Park Titration stand Rondo60/1A Position Conditioning beaker

24

M408

Barium, Ba2+

M=137.33 g/mol, z=1


Lithium sulfate, Li2SO4

c(Li2SO4) = 0.1 mol/L

Titration Excellence T50/T70/T901 Conductivity Board ME-51109840

BaCl2 + Li2SO4 = BaSO4 + 2 LiCl

Titration beakers ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Dispose as heavy metals containingaqueous solution.

Wastedisposal

Preparation and Procedures2% barium chloride solution,approx. 3-10 g

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

InLab717Indication

Barium Content of Aqueous Solutions

1) Install the InLab717 conductometric sensor by connecting itto the conductivity board (CB).

2) Perform a titer determination using 5 mL 0.1 mol/L bariumchloride standard solution.

3) Sample titration:Add 3-10 g barium standard solution into the titration beakerand dilute it with 50 mL deionized water.

4) The sample is titrated with 0.1 mol/L Li2SO4 solution.

5) The sensor is cleaned with paper tissue and rinsed withdeionized water after each titration.


2) For optimum result, the pH value of the sample solution mustbe slightly acidic to achieve complete prescipitation of bariumssulfate. If needed, the sample may be acidified by adding e.g. adilute solution of hydrochloric acid.

3) Lithium sulfate is used as a titrant since its molar conductivityis very low. Therefore, the titration curve shows a morepronounced segmented profile.

4) 0.1 mol/L Lithium sulfate:6.295 g LiSO4 * H2O (M = 127.94 g/mol) are dissolved into150 mL deionized water in a 500 mL volumetric flask. 200 mLethanol are added, and the titrant solution is filled up to the markwith deionized water.

Remarks

Content, % :R = Q*C/mC=M/(z*10)

Calculation

The barium content of an aqueous solution is determined by precipitation titration with lithium sulfate as atitrant. The conductivity of the titration is monitored by an InLab717 conductometric sensor.

Standard Barium chloride, BaCl2 , 0.1 mol/L

Albert AichertAuthor

25


All results Method-ID M408 Sample Barium chloride solution (1/1) R1 (Content) 2.026 % Sample Barium chloride solution (1/2) R1 (Content) 2.022 % Sample Barium chloride solution (1/3) R1 (Content) 2.019 % Sample Barium chloride solution (1/4) R1 (Content) 2.028 % Sample Barium chloride solution (1/5) R1 (Content) 2.031 % Sample Barium chloride solution (1/6) R1 (Content) 2.017 %


Titration curve

Results

26

Method M408 Barium content conductometric 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M408 Title Barium content conductometric Author METTLER TOLEDO Date/Time 02.08.2006 15:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Barium chloride solution Entry type Weight Lower limit 4.0 g Upper limit 10.0 g Density 1 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary



005 Titration (EQP) [1]Titrant Titrant Li2SO4

Concentration 0.1 mol/LSensor Type Conductivity Sensor InLab717 Unit μSTemperature acquisition Temperature acquisition NoStir Speed 30%Predispense Mode Volume Volume 3 mL Wait time 10 sControl Control User Titrant addition Incremental dV 0.1 mL Meas. val. acquisition Equilibrium controlled dE 1.0 μS dt 1 s t(min) 3 s t(max) 30 sEvaluation and Recognition Procedure Segmented Threshold 300 μS/mL2

Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method006 Calculation R1 Result Content Result unit % Formula R1=Q*C/m Constant C=M/(10*z) M M[Barium chloride] z z[Barium chloride] Decimal places 3 Result limits No Add. statistics functionalities No

007 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V Last titration function E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

008 End of sample

27

M409

Copper, Cu2+

M = 63.546 g/mol, z = 1

10 mL 0.6 mol/L KI solution50 mL 0.1 mol/L hydrochloric acid

Sodium thiosulfate, Na2S2O3

c(Na2S2O3) = 0.1 mol/L

Titration Excellence T50/T70/T902 additional dosing unitsRondolino Sample Changer

2 Cu2+ + 4 I- = 2 CuI + I2I2 + 2 S2O3

2- = 2 I- + S4O62-

2 DV10 and 1 DV1020 burettesTitration beaker ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Disposal as special waste(heavy metals).

Wastedisposal

Preparation and ProceduresAqueous copper solution, 3 mL(approx. conc.: 0.1 mol/L)

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM140-SC redox electrodeIndication

Copper Content in Aqueous Solutions

Note: This method allows a fully automated analysis procedureby using two additional burette drives. The method can be easilymodified for manual addition of required reagents.

1) A titer determination is first performed by using potassiumiodate (KIO3) as a primary standard: 20-30 mg KIO3 are addedto the sample and dissolved with 50 mL 0.1 mol/L hydrochloricacid. 10 mL 0.6 mol/L potassium iodide are added beforestarting titration.

2) Sample titration: 10 mL 0.6 mol/L (approx. 10%) KI solutionare added to the beaker by an additional dosing unit. This stepcan be performed manually by adding 1-2 g KI directly into thetitration beaker if no dosing unit is available.

3) 50 mL 0.1 mol/L HCl are dispensed automatically by asecond additional dosing unit. This step can be performedmanually by adding HCl directly into the beaker with a pipette.

4) Iodine is immediately generated after addition of HCl.

The sample series was analysed using a Rondolino samplechanger. The rinsing time was defined to 2 s: the electrode iscleaned with deion. water before starting next sample.

1) The method parameters have been developed and optimisedfor the samples used in this application. Thus, it may benecessary to slightly adapt the method to your specific sample.

Literature:1) Applications M509 and M510, see Titration ApplicationsBrochure 12, "30 Selected Applications", ME-51 724 765.2) Application M526, see Titration Applications Brochure 18,"Standaardisation of Titrants", ME-51 724 917.

Remarks

R1 = Q*C/m, R1: Content (g/L)C = M/z

R2 = R1*m, R2: Amount (mg)

R3 = Q*C3/m, R3: Concentr. (mol/L)C3 = 1 /z

Calculation

The determination of copper content in aqueous solutions is perfomed by titration of generated iodine withsodium thiosulfate after addition of potassium iodide to the sample.

Standard Potassium iodate, KIO3 , 20-30 mg


28


All results Method-ID M409 Sample Copper solution (1/1) R1 (Content) 6.8860 g/L R2 (Content) 20.6580 mg R3 (Concentration) 0.10836 mol/L Sample Copper solution (1/2) R1 (Content) 6.8828 g/L R2 (Content) 20.6484 mg R3 (Concentration) 0.10831 mol/L Sample Copper solution (1/3) R1 (Content) 6.8854 g/L R2 (Content) 20.6562 mg R3 (Concentration) 0.10835 mol/L Sample Copper solution (1/4) R1 (Content) 6.8785 g/L R2 (Content) 20.6355 mg R3 (Concentration) 0.10824 mol/L Sample Copper solution (1/5) R1 (Content) 6.9070 g/L R2 (Content) 20.7210 mg R3 (Concentration) 0.10869 mol/L Sample Copper solution (1/6) R1 (Content) 6.9244 g/L R2 (Content) 20.7732 mg R3 (Concentration) 0.10897 mol/L

Statistics Method-ID M409 R1 Content Samples 6 Mean 6.8940 g/L s 0.0179 g/L srel 0.259 % R2 Content Samples 6 Mean 20.6821 mg s 0.0536 mg srel 0.259 % R3 Concentration Samples 6 Mean 0.10850 mol/L s 0.00028 mol/L srel 0.261 %

Titration curve

Results

29

Method M409 Copper Content 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M409 Title Copper content Author METTLER TOLEDO Date/Time 02.08.2006 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Copper solution Entry type Fixed volume Volume 3.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C



005 Dispense (normal) [1] Titrant KI Concentration 0.6 mol/L Volume 10.0 mL Dosing rate 60.0 mL/min

006 Dispense (normal) [2] Titrant HCl Concentration 0.1 mol/L Volume 50.0 ml Dosing rate 60.0 mL/min


008 Titration (EQP) [1]Titrant Titrant Na2S2O3

Concentration 0.1 mol/LSensor Type mV Sensor DM140-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 25%Predispense Mode None Wait time 5 sControl Control User Titrant addition Dynamic dE(set value) 8.0 mV dV(min) 0.02 mL dV(max) 0.2 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 2 s t(min) 3 s t(max) 10 sEvaluation and Recognition Procedure Standard Threshold 200 mV/mL Tendency Negative Ranges 0 Add. EQP criteria No


009 Calculation R1 Result Content Result unit g/L Formula R1=Q*C/m Constant C=M/z M M[Copper] z z[Copper] Decimal places 4 Result limits No Add. statistics functionalities No

010 Calculation R2 Result Content Result unit mg Formula R2=R1*m Constant C=1 M M[Copper] z z[Copper] Result limits No Add. statistics functionalities No

011 Calculation R3 Result Content Result unit mol/L Formula R3=Q*C/m Constant C=1/z M M[Copper] z z[Copper] Result limits No Add. statistics functionalities No


013 End of sample

30

M410

Hydrogen peroxide, H2O2

M = 34.01 g/mol, z = 2

60 mL deionized water1.25 mL 20% sulfuric acid, H2SO4

Potassium permanganate, KMnO4

c(1/5 KMnO4) = 0.1 mol/L

Titration Excellence T50/T70/T901 additional dosing unit

2 MnO4- + 5 H2O2 + 6 H+ =

2 Mn2+ + 5 O2 + 8 H2O

2 DV1010 burettesTitration beaker ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Disposal as heavy metal containingaqueous solution.

Wastedisposal

Preparation and Procedures1.5 % hydrogen peroxide aqueoussolution, 0.5 mL

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM140-SC redox electrodeIndication

Hydrogen Peroxide Content in Aqueous Solutions

Note:This method allows a fully automated analysis procedure byusing one additional burette drive for dispensing.The method canbe easily modified for manual operation.

1) A titer determination is first performed by using sodiumoxalate (Na2C2O4) as a primary standard: 25-40 mg Na2C2O4

are added to the sample and dissolved with 60 mL deionizedwater. The sample solution is acidified with 1.25 mL 20%sulfuric acid.

2) Sample titration: 60 mL deionised water are added into thethe titration beaker.

3) Add 0.5 mL hydrogen peroxide solution. This step has beenperformed using an additional dosing unit. It can be performedmanually using a pipette.

4) Add 1.25 mL 20% sulfuric acid (H2SO4) to the titrationbeaker. This step has been performed using an additionaldosing unit. If this is not possible, this step can be performedmanually using a pipette.

1) The method parameters have been developed and optimisedfor the sample used in this application. Thus, it may benecessary to slightly adapt the method to your specific sample.

Literature:

1) Application M527, see Titration Applications Brochure 12,"30 Selected Applications", ME-51 724 765.2) Application M158,"Determination of Ammonia and Hydrogen Peroxide",www.mt.com .

Remarks

R1: Content (%)

R1 = Q*C/m,C = M/(10*z) ; z = 2

Calculation

The hydrogen peroxide content in aqueous solutions is perfomed by redox titration with potassiumpermanganate.

Standard Sodium oxalate, Na2C2O4, 25-40 mg

Claudia SchreinerAuthor

31


All results Method-ID M410 Sample Hydrogen peroxide solution (1/1) R1 (Content) 1.515 % Sample Hydrogen peroxide solution (1/2) R1 (Content) 1.516 % Sample Hydrogen peroxide solution (1/3) R1 (Content) 1.515 % Sample Hydrogen peroxide solution (1/4) R1 (Content) 1.516 % Sample Hydrogen peroxide solution (1/5) R1 (Content) 1.525 % Sample Hydrogen peroxide solution (1/6) R1 (Content) 1.517 % Sample Hydrogen peroxide solution (1/7) R1 (Content) 1.518 %


Titration curve

Results

32

Method M410 Hydrogen peroxide content 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M410 Title Hydrogen peroxide content Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Hydrogen peroxide solution Entry type Fixed volume Volume 0.5 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C


004 Dispense (normal) [1] Titrant 20% H2SO4

Concentration 1 Volume 1.25 ml Dosing rate 60.0 mL/min


006 Titration (EQP) [1]Titrant Titrant 1/5 KMnO4

Concentration 0.1 mol/LSensor Type mV Sensor DM140-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode Volume Volume 2 mL Wait time 30 sControl Control User Titrant addition Dynamic dE(set value) 8.0 mV dV(min) 0.02 mL dV(max) 0.2 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 1 s t(min) 3 s t(max) 10 sEvaluation and Recognition Procedure Standard Threshold 200 mV/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 10 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method007 Calculation R1 Result Content Result unit % Formula R=Q*C/m Constant C=M/(10*z) M M[H2O2] z z[H2O2] Decimal places 3 Result limits No Add. statistics functionalities No


009 End of sample

33

M411

L(+) ascorbic acid, C6H8O6

M=176.13 g/mol, z=2

50 mL deionized water2% oxalic acid for adjustment to pH 3

2,6-dichlorophenolindophenol, DPIc(1/2 DPI) = 0.01 mol/L


L(+)-ascorbic acid is oxidized by DPI:C6H6O6-H2 + DPI = C6H6O6 + H2-DPI

Oxidation:C6H8O6 = C6H6O6 + 2H+ + 2e-

One additional DV1010 glass buretteTitration beaker ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Neutralize before final disposal asaqueous solution.

Wastedisposal

Preparation and Procedures5 g orange juiceSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Vitamin C Content in Orange Juice: Voltametric Indication

Note:- The DPI titrant has to be prepared fresh daily. It has to bestored in brown glass bottles to protect it from light.- Ascorbic acid is sensitive to light, temperature and oxygen.Titration beakers with light protection as well as use of purgegas are recommended. Keep in the dark.- Ascorbic acid solution has to be prepared fresh prior to use.

1) Titrant preparation:0.36 g DPI sodium salt monohydrate (M = 290.08 g/mol) isweighed in a 250 mL volumetric flask and filled up with deion.water to obtain a titrant concentration c(1/2 DPI) = 0.01 mol/L.The flask was placed in an unltrasonic bath during 10 min. toimprove solubility.

2) The titer is determined using L(+) ascorbic acid:5 mL 0.01 mol/L standard solution are added into a titrationbeaker and diluted with 50 mL deionized water. The pH value isadjusted to pH 3 with 2% oxalic acid by titrating the sampleusing an EP titration function.

3) The juice is well homogenized and is weighed directly intothe titration beaker, without special treatment such as filtration.After addition of 50mL deionised water the sample can bepurged with nitrogen gas to avoit oxidation of Vitamin C.


2) The sample size depends on the amount of vitamin C: 1-15mg vitamin C correspond 0.5 - 8.5 mL 0.01 mol/L 1/2 DPI.

3) If DPI sodium salt dihydrate (M=308.08 g/mol) is used, anexcess has to be weighed in due to its bad solubility. The titranthas to be filtrated prior to use.

4) Both DPI titrant and ascorbic acid standard solution are notstable. To get accurate results, It is recommended to preparethem fresh before use.

5) Orange juice was stored in the refrigerator when not used.

6) This method describes the voltametric determination of L(+)ascorbic acid with a polarized sensor DM143-SC. An alternatingcurrent of 10-12 μA is applied to the double pin platinumelectrode and the potential is measured.


Remarks

R1=Q*C/m; Content (mg/100g)C=100*M/z

R2=Q*C/m; Content (%)C=M/(10*z)

Calculation

Content determination of vitamin C (ascorbic acid) in orange juice by voltametric titration with DPI. Thetitration is monitored by a polarized DM143 electrode.

Standard Ascorbic acid, 0.01 mol/L

Thomas HitzAuthor

34


All results Method-ID M411 Sample Orange juice (1/1) R1 (Content) 34.713 mg/100 g R2 (Content) 0.0347 % Sample Orange juice (1/2) R1 (Content) 34.227 mg KOH/g R2 (Content) 0.0342 % Sample Orange juice (1/3) R1 (Content) 34.887 mg/100 g R2 (Content) 0.0349 % Sample Orange juice (1/4) R1 (Content) 35.367 mg/100 g R2 (Content) 0.0354 % Sample Orange juice (1/5) R1 (Content) 34.896 mg/100 g R2 (Content) 0.0349 %

Statistics Method-ID M411 R1 Content Samples 5 Mean 34.816 mg/100 g s 0.334 mg/100 g srel 0.960 % R2 Content Samples 5 Mean 0.0348 % s 0.0004 % srel 0.960 %

Titration curve

Results

35

Method M411 Vitamin C content voltametric 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M411 Title Vitamin C content voltametric Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Orange juice Entry type Weight Lower limit 0.0 g Upper limit 10.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary

003 Titration stand (Manual stand) Type Manual stand Titration stand Manual Stand 1


005 Titration (EQP) [1]Titrant Titrant 1/2 DPI Concentration 0.01 mol/LSensor Type Polarized Sensor DM143-SC Unit mV Indication Voltametric Ipol 12 μATemperature acquisition Temperature acquisition NoStir Speed 35 %Predispense Mode Volume Volume 1.0 mL Wait time 2 sControl Control User Titrant addition Incremental dV 0.05 mL Meas. value acquisition Equilibrium controlled dE 2.0 mV dt 1 s t(min) 2 s t(max) 30 sEvaluation and recognition Procedure Standard Threshold 500 mV/mL Tendency Negative Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

006 Calculation R1 Result Content Result unit mg/100g Formula R1=Q*C/m Constant C=100*M/z M M[Ascorbic acid] z z[Ascorbic acid] Decimal places 3 Result limits No Add. statistics functionalities No

Method007 Calculation R2 Result Content Result unit % Formula R2=Q*C/m Constant C=M/(10*z) M M[Ascorbic acid] z z[Ascorbic acid] Decimal places 4 Result limits No Add. statistics functionalities Yes


009 End of sample

36

M412

L(+) ascorbic acid, C6H8O6

M=176.13 g/mol, z=2

50 mL deionized water2% oxalic acid for adjustment to pH 3

2,6-dichlorophenolindophenol, DPIc(1/2 DPI) = 0.01 mol/L


L(+)-ascorbic acid is oxidized by DPI:C6H6O6-H2 + DPI = C6H6O6 + H2-DPI

Oxidation:C6H8O6 = C6H6O6 + 2H+ + 2e-

One additional DV1010 glass buretteTitration beaker ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO


Wastedisposal

Preparation and Procedures5 g orange juiceSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Vitamin C Content in Orange Juice: Amperometric Indication

Note:- The DPI titrant has to be prepared fresh daily. It has to bestored in brown glass bottles to protect it from light.- Ascorbic acid is sensitive to light, temperature and oxygen.Titration beakers with light protection as well as use of purgegas are recommended. Keep in the dark.- Ascorbic acid solution has to be prepared fresh prior to use.

1) Titrant preparation:0.36 g DPI sodium salt monohydrate (M = 290.08 g/mol) isweighed in a 250 mL volumetric flask and filled up with deion.water to obtain a titrant concentration c(1/2 DPI) = 0.01 mol/L.The flask was placed in an unltrasonic bath during 10 min. toimprove solubility.

2) The titer is determined using L(+) ascorbic acid:5 mL 0.01 mol/L standard solution are added into a titrationbeaker and diluted with 50 mL deionized water. The pH value isadjusted to pH 3 with 2% oxalic acid by titrating the sampleusing an EP titration function.

3) The juice is well homogenized and is weighed directly intothe titration beaker, without special treatment such as filtration.After addition of 50mL deionised water the sample can bepurged with nitrogen gas to avoit oxidation of Vitamin C.


2) The sample size depends on the amount of vitamin C: 1-15mg vitamin C correspond 0.5 - 8.5 mL 0.01 mol/L 1/2 DPI.

3) If DPI sodium salt dihydrate (M=308.08 g/mol) is used, anexcess has to be weighed in due to its bad solubility. The titranthas to be filtrated prior to use.

4) Both DPI titrant and ascorbic acid standard solution are notstable. To get accurate results, It is recommended to preparethem fresh before use.

5) Orange juice was stored in the refrigerator when not used.

6) This method describes the amperometric determination ofL(+) ascorbic acid with a polarized sensor DM143-SC. Apolarization current of 200 mV is applied to the double pinplatinum electrode and the current is monitored during titration.


Remarks

R1=Q*C/m; Content (mg/100g)C=100*M/z

R2=Q*C/m; Content (%)C=M/(10*z)

Calculation

Content determination of vitamin C (ascorbic acid) in orange juice by amperometric titration with DPI. Thetitration is monitored by a polarized DM143 electrode.

Standard Ascorbic acid, 0.01 mol/L


37


All results Method-ID M412 Sample Orange juice (1/1) R1 (Content) 24.0989 mg/100 g Sample Orange juice (1/2) R1 (Content) 23.9783 mg/100 g Sample Orange juice (1/3) R1 (Content) 24.5614 mg/100 g Sample Orange juice (1/4) R1 (Content) 23.5523 mg/100 g Sample Orange juice (1/5) R1 (Content) 23.5976 mg/100 g Sample Orange juice (1/6) R1 (Content) 24.3256 mg/100 g

Statistics Method-ID M412 R1 Content Samples 6 Mean 24.0190 mg/100 g s 0.3979 mg/100 g srel 1.657 %

Titration curve

Results

38

Method M412 Vitamin C content amperometric 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M412 Title Vitamin C contentamperometric Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Orange juice Entry type Weight Lower limit 0.0 g Upper limit 10.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary

003 Titration stand (Manual stand) Type Manual stand Titration stand Manual Stand 1


005 Titration (EQP) [1]Titrant Titrant 1/2 DPI Concentration 0.01 mol/LSensor Parameters Type Polarized Sensor DM143-SC Unit μA Indication Amperometric Upol 200 mVTemperature acquisition Temperature acquisition NoStir Speed 30 %Predispense Mode None Wait time 0 sControl Control User Titrant addition Incremental dV 0.1 mL Meas. value acquisition Equilibrium controlled dE 0.3 μA dt 2 s t(min) 5 s t(max) 30 sEvaluation and recognition Procedure Segmented Threshold 1 μA/mL2

Ranges 1 Lower limit 0.6 μA Upper limit 10.0 μA Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method006 Calculation R1 Result Content Result unit mg/100g Formula R=Q*C/m Constant C=100*M/z M M[Ascorbic acid] z z[Ascorbic acid] Decimal places 4 Result limits No Add. statistics functionalities No

007 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V Last titration function E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

009 End of sample

39

M413

Sodium dodecyl sulfate, C12H25NaO4SM = 288.38 g/mol, z = 1

60 mL deionised water

Hyamine 1622, C27H42ClNO2

c(Hyamine) = 0.004 mol/L


Simplified scheme:C27H42NO2

+ + C12H25O4S - =C27H42NO2-C12H25O4S

1 DV1010 buretteTitration beaker ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Disposal as aqueous solution; a specialtreatment is not necessary

Wastedisposal

Preparation and Procedures5 mL liquid detergent solution,approx. 8 g/L

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DP5 PhototrodeTM , 550 nmIndication

Anionic Surfactant Content in Liquid Detergents by Turbidimetric Titration

1) The titer determination is performed by titrating 1 mL 0.01mol/L SDS, which are diluted with 60 mL deionized water.

2) Sample titration:5 mL of an aqueous solution of liquid detergent are added intothe titration beaker and diluted with 60 mL deionised water.

3) The concentration of the liquid detergent solution was chosento get an approx. titrant consumption of 5 mL. Its value is storedas auxiliary value H[SDS] in g/mL.

4) Preparation of the liquid detergent solution: Approx. 8 gliquid detergent are given into 1 L volumetric flask. The flask isfilled up with deionised water (here: 8.5856 g liq. detergent,which gives a content of 0.0429 g/5 mL)

5) The sample series was analysed using a Rondolino samplechanger. The conditioning time was set to 30 s (Rondolinosettings: 4) to clean the electrode with deionized water beforestarting the subsequent sample.

1) After turning on the phototrode, wait for 15-10 minutes beforestarting analysis to achieve a stable light intensity. Check thetransmission signal of the phototrode in deionised water and setit to 1000 mV by turning the knob on the top of it.

2) Avoid the formation of air bubbles during titration since theydisturb the photometric indication. Thus, select the appropriatestirring speed.


4) This method allows a fully automated analysis procedurewith a Rondolino sample changer. The method can be easilymodified for manual operation. Select "Manual stand" in themethod function "Titration stand".

Literature:

1) Application M549, see Titration Applications Brochure 18,"Standardisation of Titrants", ME-51 724 917.2) Titration Applications Brochure 22,"Surfactant Titration", ME-51 725 015 .

Remarks

R1: SDS-Content (%)

R1 = Q*C/m,C = M/(10*z) ; z = 1

Calculation

The anionic surfactant content in liquid dish washer as SDS content (sodium dodecyl sulfate, or sodiumlauryl sulfate) is determined by precipitation titration with Hyamine 1622, a cationic surfactant. The turbidityincrease during titration is monitored by the DP5 PhototrodeTMat 550 nm.

Standard SDS, 1 mL 0.01 mol/L, see M549


40


All results Method-ID M413 Sample Liquid detergent solution (1/1) R1 (Content) 13.91 % Sample Liquid detergent solution (1/2) R1 (Content) 13.89 % Sample Liquid detergent solution (1/3) R1 (Content) 13.83 % Sample Liquid detergent solution (1/4) R1 (Content) 13.91 % Sample Liquid detergent solution (1/5) R1 (Content) 13.90 % Sample Liquid detergent solution (1/6) R1 (Content) 13.83 %


Titration curve

Results

41

Method M413 SDS content photometric 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M413 Title SDS content photometric Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Liquid detergent solution Entry type Fixed volume Volume 5.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C



005 Titration (EQP) [1]Titrant Titrant Hyamine 1622 Concentration 0.004 mol/LSensor Type Phototrode Sensor DP5 Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode Volume Volume 4.5 mL Wait time 15 sControl Control User Titrant addition Incremental dV 0.1 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 1 s t(min) 3 s t(max) 10 sEvaluation and Recognition Procedure Standard Threshold 200 mV/mL Tendency Negative Ranges 0 Add. EQP criteria NoTermination At Vmax 10 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method006 Calculation R1 Result Content Result unit % Formula R1=Q*C/(m*H[SDS]) Constant C=M/(10*z) M M[Sodium dodecylsulfate] z z[Sodium dodecylsulfate] Decimal places 2 Result limits No Add. statistics functionalities No


008 End of sample

42

M414







+ + C12H25O4S - =C27H42NO2-C12H25O4S

1 DV1010 buretteTitration beaker ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Disposal as aqueous solution; a specialtreatment is not necessary

Wastedisposal


Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DS500 Surfactant Sensitive ElectrodeDX200 Ref. electrode (1 M KNO3)

Indication

Anionic Surfactant Content in Liquid Detergents by Potentiometric Titration

1) The titer determination is performed by titrating 1 mL 0.01mol/L SDS, which are diluted with 60 mL deionized water.

2) Sample titration:5 mL of an aqueous solution of liquid detergent are added intothe titration beaker and diluted with 60 mL deionised water.

3) The concentration of the liquid detergent solution was chosento get an approx. titrant consumption of 5 mL. Its value is storedas auxiliary value H[SDS] in g/mL.

4) Preparation of the liquid detergent solution: Approx. 8 gliquid detergent are given into 1 L volumetric flask. The flask isfilled up with deionised water (here: 8.0482 g liq. detergent,which gives a content of 0.0402 g/5 mL)

5) The sample series was analysed using a Rondolino samplechanger. The conditioning time was set to 30 s (Rondolinosettings: 4) to clean the electrode with deionized water beforestarting the subsequent sample.

6) Before starting the sample series it is recommended tocondition the DS500 electrode by running a trial titration withSDS or the liquid detergent.


2) DS500 surfactant sensitive electrode:- Fill the DS500-ISE and the electrode tip with the electrolyte.- Screw the electrode tip onto the shaft.- Shake the DS500 2-3 times to avoid the presence of airbubbles into the electrode tip. Rinse it with deion. water.- Condition it in 0.01 mol/L SDS solution for 20-30 minutes.

3) This method allows a fully automated analysis procedurewith a Rondolino sample changer. The method can be easilymodified for manual operation. Select "Manual stand" in themethod function "Titration stand".

4) The conditioning time was set to 30 s (Rondolino settings: 4)to clean the electrode with deionized water before starting thesubsequent sample.

Literature:

1) Application M610, Titration Applications Brochure 22,"Surfactant Titration", ME-51 725 015 .

Remarks

R1: SDS-Content (%)

R1 = Q*C/m,C = M/(10*z) ; z = 1

Calculation

The anionic surfactant content in liquid dish washer as SDS content (sodium dodecyl sulfate, sodium laurylsulfate) is determined by precipitation titration with Hyamine 1622, a cationic surfactant. The potentialchange during titration is monitored by the DS500 surfactant sensitive electrode.

Standard SDS, 1 mL 0.01 M aliquot, see M610


43




Titration curve

Results

44

Method M414 SDS content potentiometric 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M414 Title SDS content potentiometric Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Liquid detergents olution Entry type Fixed volume Volume 5.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C



005 Titration (EQP) [1]Titrant Titrant Hyamine 1622 Concentration 0.004 mol/LSensor Type mV Sensor DS500 Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode Volume Volume 2 mL Wait time 15 sControl Control User Titrant addition Dynamic dE(set value) 8.0 mV dV(min) 0.02 mL dV(max) 0.2 mL Meas. val. acquisition Equilibrium controlled

dE 1.0 mVdt 2 st(min) 5 st(max) 30 s

Evaluation and Recognition Procedure Standard Threshold 50 mV/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 10 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No



008 End of sample

45

M415

--

--

Hydrochloric acid, HClc(HCl) = 0.1 mol/L


HCl + NaOH = NaCl + H2OHCl + CO3

2- = HCO3- + Cl-

HCl + HCO3- = CO2 + H2O + Cl-

1 DV1010 buretteTitration beakers ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Neutralize the slightly acid waste beforedisposal.

Wastedisposal

Preparation and Procedures50 mL tap waterSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG115-SCIndication

m-Value of Tap Water

Note: This method allows a fully automated analysis procedureby using a Rondolinos sample changer. The method can beeasily modified for manual operation. Select "Manual stand" inthe method function "Titration stand".

1) Before the analysis an electrode calibration was performedusing METTLER TOLEDO buffers of pH 4.01, 7.00 and 9.21.

2) Fill a (preferably) PE bottle to the brim with the water to beanalyzed. Keep it closed and at sampling temperature.

3) Pipette 50 mL into the beaker shortly before titration.

4) For best results, if the initial pH lies close to the end potential,use a lower concentration of the corresponding titrant.

5) The samples were analysed using a Rondolino samplechanger. The electrode was rinsed during 2 s and conditionedduring 10 s (Rondolino settings: 6). In this way, the electrode iscleaned with deionised water before starting the subsequentsample.

1) The method parameters have been optimised for the sampleused in this application. It may be necessary to slightly adaptthe method to your specific sample.

2) The acid capacity allows surface waters to resist sudden pHchanges due to e.g. organic acid waste, groundwater dischargeor industrial waste, or due to sources such as bacteria, Fe3+,hydrated Al3+, H2S, fatty acids, proteins, CO2.

3) The acid capacity depends on the equilibrium of free CO2,bicarbonate HCO3

-, and carbonate CO32- in the corresponding

water and therefore on its temperature.Mineral weathering buffers groundwaters, e.g. limestone rockCaCO3 (s) + CO2 (g) = Ca2+ (aq) + 2 HCO3

- (aq)The bicarbonate ion then acts as a base to neutralize acids:HCO3

- (aq) + H+ (aq) = CO2 (g) + H2O (l)

4) The m-value (total alkalinity) represents the acid neutralizingcapacity and is determined in e.g. drinking water. Acidity canaffect corrosion, soil leaching, and aquatic life in general. Thename originates from the methyl orange color indicator (red toyellow-orange at pH 4.3) formerly used.References:http://nas.cl.uh.edu/zhang/3431_04S/05_Acid-Base.ppt

Remarks

Total alkalinity or methyl orangealkalinity (m-value) is expressed asmmol/L or mg/L CaCO3

Calculation

The m value of water is determined by an endpoint titration to pH 4.30 with hydrochloric acid.

Standard Tris(hydroxymethyl)-aminomethane, 50-100 mg


46


All results Method-ID M415 Sample Tap water (1/1) R1 (Content) 3.005 mmol/L Sample Tap water (1/2) R1 (Content) 2.991 mmol/L Sample Tap water (1/3) R1 (Content) 2.992 mmol/L Sample Tap water (1/4) R1 (Content) 2.993 mmol/L Sample Tap water (1/5) R1 (Content) 2.996 mmol/L Sample Tap water (1/6) R1 (Content) 2.992 mmol/L

Statistics Method-ID M415 R1 Content Samples 6 Mean 2.995 mmol/L s 0.005 mmol/L srel 0.176 %

Titration curve

Results

47

Method M415 m-value of tap water 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M415 Title m-Value of tap water Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Tap water Entry type Fixed volume Volume 100 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C



005 Titration (EP) [1]Titrant Titrant HCl Concentration 0.1 mol/LSensor Type pH Sensor DG115 Unit pHTemperature acquisition Temperature acquisition NoStir Speed 50 %Predispense Mode None Wait time 0 sControl Control User End point type Absolute Tendency Negative Endpoint value 4.30 pH Control band 3.0 pH Dosing rate (max) 10 mL/min Dosing rate (min) 10 μL/minTermination At EP Yes Tuermination delay 10 s At Vmax 10.0 mL Max. time Infinity

006 Calculation R1 Result Content Result unit mmol/L Formula R1=Q*C/m Constant C=1000 M M[None] z z[None] Decimal places 3 Result limits No Add. statistics functionalities No

007 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

008 End of sample

Method

48

M416

--

--

Sodium hydroxide, NaOHc(HCl) = 0.01 mol/L


HCl + NaOH = NaCl + H2O

1 DV1010 buretteTitration beakers ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Neutralize the slightly alkaline wastebefore disposal.

Wastedisposal

Preparation and Procedures100 mL tap waterSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG115-SCIndication

p-Value of Tap Water

Note: This method allows a fully automated analysis procedureby using a Rondolino sample changer. The method can beeasily modified for manual operation. Select "Manual stand" inthe method function "Titration stand".

1) Before the analysis an electrode calibration was performedusing METTLER TOLEDO buffers of pH 4.01, 7.00 and 9.21.

2) Fill a (preferably) PE bottle to the brim with the water to beanalyzed. Keep it closed and at sampling temperature.

3) Pipette 50 mL into the beaker shortly before titration.


5) The samples were analysed using a Rondolino samplechanger. The electrode was rinsed during 2 s and conditionedduring 10 s (Rondolino settings: 6). In this way, the electrode iscleaned with deionised water before starting the subsequentsample.


2) The p-value (total acidity) represents the base neutralizingcapacity of a water and is determined in many different samples,e.g. drinking water, wastewater, caustic wash solutions.

3) The pH value and the base capacity depend on theequilibrium of free CO2, bicarbonate HCO3

-, and carbonate CO32-

in the corresponding water and therefore on its temperature.

4) The name p-value originates from the phenolphthalein colorindicator (colorless to pink at pH 8.2 and above) formerly used.

References:http://nas.cl.uh.edu/zhang/3431_04S/05_Acid-Base.ppt

Remarks

Total acidity or phenolphtalein acidity(p-value) is expressed as mmol/L ormg/L CaCO3

Calculation

The p-value of water is determined by an endpoint titration to pH 8.20 with sodium hydroxide.

Standard Potassium hydrogen phthalate, 70-120 mg


49


All results Method-ID M416 Sample Tap water (1/1) R1 (Content) 0.229 mmol/L Sample Tap water (1/2) R1 (Content) 0.220 mmol/L Sample Tap water (1/3) R1 (Content) 0.234 mmol/L Sample Tap water (1/4) R1 (Content) 0.217 mmol/L Sample Tap water (1/5) R1 (Content) 0.237 mmol/L Sample Tap water (1/6) R1 (Content) 0.214 mmol/L

Statistics Method-ID M416 R1 Content Samples 6 Mean 0.225 mmol/L s 0.019 mmol/L srel 4.190 %

Titration curve

Results

50

Method M416 p-Value of tap water (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M416 Title p-Value of tap water (EP) Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Tap water Entry type Fixed volume Volume 100 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C



005 Titration (EP) [1]Titrant Titrant NaOH Concentration 0.01 mol/LSensor Type pH Sensor DG115 Unit pHTemperature acquisition Temperature acquisition NoStir Speed 50 %Predispense Mode None Wait time 0 sControl Control User End point type Absolute Tendency Positive Endpoint value 8.20 pH Control band 3.0 pH Dosing rate (max) 10 mL/min Dosing rate (min) 10 μL/minTermination At EP Yes Termination delay 0 s At Vmax 10.0 mL Max. time Infinity

006 Calculation R1 Result Content Result unit mmol/L Formula R1=Q*C/m Constant C=1000 M M[None] z z[None] Decimal places 3 Result limits No Add. statistics functionalities No

007 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

008 End of sample

Method

51

M417

Acid neutralizing substances(e.g. CaCO3)


Hydrochloric acid, HClc(HCl) = 0.1 mol/L



NaOH represents the acid neutralizingcomponents:

1 DV1010 BuretteTitration beakers ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Neutralize the acid waste beforedisposal.

Wastedisposal

Preparation and Procedures0.03-0.08 g antacid tabletSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG111-SCIndication

pH-Stat Titration of Antacid at pH 3

1) The titer is determined by dissolving 50 mgTris-(hydroxymethyl)-aminomethane (THAM) as a primarystandard in 50 mL deionized water.

2) Before analysis an electrode calibration is performed usingMETTLER TOLEDO buffers of pH 4.01, 7.00 and 9.21.If there is no automatic temperature compensation, enter thecorrect temperature manually.

3) An antacid tablet is crushed and 30-80 mg are added into atitration beaker. 50 mL deionized water are added to dissolve it.

4) The electrode is rinsed with deionised water before startingthe subsequent sample.



References:- METTLER TOLEDO Titration Applications Brochure Nr. 2,"Various methods", ME-724 557- METTLER TOLEDO Application M054,"pH-Stat of Antacids at pH 3"

Remarks

See methodCalculation

The neutralizing capacity in antacid tablet is tested by constantly maintaining the pH value at pH 3.0 using apH-Stat titration with HCl as a titrant.

Standard THAM, 50-80 mg


52


All results Method-ID M417 Sample Antacid solution (1/1) R1 (Content) 1024.911 mg/g R2 (Consumption) 0.213 mL/min R3 (corr. coeff. (0,2)) 0.980 R4 (% turnover after 2 min.) 42.691 % R5 (time to 50% titr. conversion) 2.612 min Sample Antacid solution (1/2) R1 (Content) 1016.914 mg/g R2 (Consumption) 0.118 mL/min R3 (corr. coeff. (0,2)) 0.973 R4 (% turnover after 2 min.) 39.445 % R5 (time to 50% titr. conversion) 3.668 min Sample Antacid solution (1/3) R1 (Content) 1019.263 mg/g R2 (Consumption) 0.191 mL/min R3 (corr. coeff. (0,2)) 0.989 R4 (% turnover after 2 min.) 40.284 % R5 (time to 50% titr. conversion) 2.728 min Sample Antacid solution (1/4) R1 (Content) 1024.219 mg/g R2 (Consumption) 0.133 mL/min R3 (corr. coeff. (0,2)) 0.981 R4 (% turnover after 2 min.) 38.128 % R5 (time to 50% titr. conversion) 3.333 min Sample Antacid solution (1/5) R1 (Content) 107.495 mg/g R2 (Consumption) 0.261 mL/min R3 (Corr. coeff. (0,2)) 0.977 R4 (% turnover after 2 min.) 42.182 % R5 (time to 50% titr. conversion) 2.753 min

Statistics Method-ID M417 R1 Content Samples 5 Mean 1020.560 mg/g s 3.765 mg/g srel 0.37 %

Titration curve

Results

53

Method M417 Antacid (Stating) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M417 Title Antacid (Stating) Author METTLER TOLEDO Date/Time 02.08.2006 15:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Antacid solution Entry type Weight Lower limit 0.03 g Upper limit 0.08 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary



005 Stating [1]Titrant Titrant HCl Concentration 0.1 mol/LSensor Parameters Type pH Sensor DG111-SC Unit pHTemperature acquisition Temperature acquisition NoStir Speed 35 %Pretitration Pretitration Yes Control band 2.0 pHPredispense Mode None Wait time 0 sControl Set potential 3.0 pH Control band 0.01 pH Tendency Negative Dosing rate (max) 10 mL/min Dosing rate (min) 10 μL/minMonitoring Monitoring NoTermination At Vmax 8.5 mL From t(min) No At t(max) Yes t(max) 20 min After stating duration No At minimum rate Yes dV 0.01 mL dt 1 minMeasured value storage Interval 5 s Start condition After pretitration

006 Calculation R1 Result Content Result unit mg/g Formula R1=QStt(tCON(100))*C/m Constant C=M/z M M[Calcium carbonate] z z[Calcium carbonate] Decimal places 3 Result limits No Additional statistics functionalities No

Method007 Calculation R2 Result Mean consumption Result unit mL/min Formula R2=CVt(0,tCON(100)) Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Additional statistics functionalities No

008 Calculation R3 Result Correlation coefficient Result unit -- Formula R3=CORRt(0,2) Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Additional statistics functionalities No

009 Calculation R4 Result Turnover after 2 minutes Result unit % Formula R4=CONt(2) Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Additional statistics functionalities No

010 Calculation R5 Result Time to 50% titrant conversion Result unit min Formula R5=tCON(50) Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Additional statistics functionalities No

011 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t Last titration function V - t Last titration function dV/dt - t Last titration function T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No Condition No

012 End of sample

54

M418

Hydrochloric acid, HClM = 36.46 g/mol, z = 1


Sodium hydroxide, NaOHc(HCl) = 0.1 mol/L



1 DV1010 BuretteTitration beakers ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Neutralize the slightly alkaline wastebefore disposal.

Wastedisposal

Preparation and Procedures5 mL hydrochloric acid solution, HClc(HCl) = 0.01 mol/L

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG111-SCIndication

Hydrochloric Acid Content by Endpoint Titration

1) Before analysis an electrode calibration was performed usingMETTLER TOLEDO buffers of pH 4.01, 7.00 and 9.21.

2) The titer determination is performed by titrating potassiumhydrogen phthalate (KHP) as a primary standard: 70-120 mgKHP are dissolved with 50 mL deionized water into a titrationbeaker.

3) Sample titration:5 mL 0.1 mol/L hydrochloric acid solution are transferred into atitration beaker with a pipette.

4) 50 mL deionised water are added into a titration beaker todilute the sample.


Remarks

R1 = Q , consumption, mmol

R2 = Q*C/m , content, g/LC=M/z

Calculation

The content of hydrochloric acid in water is determined by potentiometric endpoint titration to pH 8.3 withsodium hydroxide.

Standard Potassium hydrogen phthalate, 70-120 mg


55


All results Method-ID M418 Sample HCl content (EP) (1/1) R1 (Consumption) 0.511 mmol R2 (Content) 3.725 g/L Sample HCl content (EP) (1/2) R1 (Consumption) 0.509 mmol R2 (Content) 3.710 g/L Sample HCl content (EP) (1/3) R1 (Consumption) 0.510 mmol R2 (Content) 3.717 g/L Sample HCl content (EP) (1/4) R1 (Consumption) 0.510 mmol R2 (Content) 3.717 g/L Sample HCl content (EP) (1/5) R1 (Consumption) 0.508 mmol R2 (Content) 3.701 g/L Sample HCl content (EP) (1/6) R1 (Consumption) 0.512 mmol R2 (Content) 3.730 g/L


Method-ID M418 R2 Content Samples 6 Mean 3.717 g/L s 0.010 g/L srel 0.279 %

Titration curve

Results

56

Method M418 HCl content (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M418 Title HCl content (EP) Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 HCl solution Entry type Fixed volume Volume 5.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C



005 Titration (EP) [1]Titrant Titrant NaOH Concentration 0.1 mol/LSensor Type pH Sensor DG111-SC Unit pHTemperature acquisition Temperature acquisition NoStir Speed 30 %Predispense Mode Volume Volume 2.0 mL Wait time 10 sControl Control User End point type Absolute Tendency Positive Endpoint value 8.30 pH Control band 3.0 pH Dosing rate (max) 5 mL/min Dosing rate (min) 5 μL/minTermination At EP Yes Termination delay 10 s At Vmax 10.0 mL Max. time Infinity

006 Calculation R1 Result Consumption Result unit mmol Formula R1=Q Constant C=1 M M[Hydrochloric acid] z z[Hydrochloric acid] Decimal places 3 Result limits No Add. statistics functionalities No

Method007 Calculation R2 Result Content Result unit g/L Formula R2=Q*C/m Constant C=M/z M M[Hydrochloric acid] z z[Hydrochloric acid] Decimal places 3 Result limits No Add. statistics functionalities No


009 End of sample

57

M419

Sulphur dioxide, SO2

M = 64.06 g/mol, z = 2

5 mL 10% potassium iodide, KI5 mL 20% sulfuric acid, H2SO4

Iodine, I2c(1/2 I2) = 0.02 mol/L

Titration Excellence T50/T70/T90Manual standTwo additional burette drives

SO2 + I2 + 2 H2O = H2SO4 + 2 HI

3 DV1010 BurettesTitration beakers ME-101974XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Neutralize the acid waste before finaldisposal.

Wastedisposal

Preparation and Procedures50 mL white wineSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Free Sulphur Dioxide (SO2) Content in Wine

Note: This method allows a fully automated analysis procedureby using two additional burette drives.

1) The titer determination is performed using pure ascorbic acidas a primary standard.

2) Sample determination: 50 mL wine are transferred into atitration beaker with a pipette.

3) 5 mL 10% potassium iodide solution are added. This stephas been performed using an additional dosing unit. It can beperformed manually using a pipette.

4) 5 mL 20% sulfuric acid are added to the titration beaker.This step has been performed using an additional dosing unit. Ifnot possible, this step can be done manually with a pipette.

Note:Sodium metabisulfite (Na2S2O5, M = 222.32 g/mol) can beused as a SO2-Standard (1 Na2S2O5 --> 2 SO2 ).


2) In order to avoid loss of SO2, the samples must be taken froma freshly openend bottle. After opening the bottle, free SO2 canevaporate with CO2 or be oxidized while in contact with airresulting in too low results. Working with the sample changerleads to SO2 losses from the sample beakers already preparedon the rack. Therefore it is recommended to work manually.

3) Iodine is also reduced by other wine components. Thesecompeting reactions can partly be delayed by the addition of 5mL 10% potassium iodide solution.

4) The reaction only takes place in acidic medium. Therefore, 5mL 20% H2SO4 must be added immediately before titration.

5) If the sample contains ascorbic acid the amount of SO2 willbe higher, because of the reaction from ascorbic acid withiodine.

Remarks

R = Q*C/m , content, mg/LC = M*1000/z

Calculation

The content of free sulphur dioxide (SO2) in wine is determined by redox titration with iodine as a titrant. Thetitration is monitored using a Pt double pin electrode DM143 at a fixed polarization current (voltametricindication)

Standard Ascorbic acid, C6H8O6, M=176.13


58


All results Method-ID M419 Sample White wine (1/1) R1 (Content) 21.222 mg/L Sample White wine (1/2) R1 (Content) 21.294 mg/L Sample White wine (1/3) R1 (Content) 21.160 mg/L Sample White wine (1/4) R1 (Content) 21.114 mg/L Sample White wine (1/5) R1 (Content) 21.190 mg/L Sample White wine (1/6) R1 (Content) 21.127 mg/L

Statistics Method-ID M419 R1 Content Samples 6 Mean 21.185 mg/L s 0.067 mg/L srel 0.315 %

Titration curve

Results

59

Method M419 Free SO2 in wine (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M419 Title HCl content Author METTLER TOLEDO Date/Time 02.08.200 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 White wine Entry type Fixed volume Volume 50.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C


004 Dispense (normal) [1] Titrant 10% KI Concentration 1 Volume 5.0 mL Dosing rate 60.0 mL/min

005 Dispense (normal) [2] Titrant 20% H2SO4

Concentration 1 Volume 5.0 mL Dosing rate 60.0 mL/min


007 Titration (EP) [1]Titrant Titrant 1/2 I2

Concentration 0.02 mol/LSensor Type Polarized Sensor DM143 Unit mV Indication Voltametric Ipol 10 μATemperature acquisition Temperature acquisition NoStir Speed 50 %Predispense Mode No Wait time 10 sControl Control User Endpoint type Absolute Tendency Negative Endpoint value 100 mV Control band 30 mV Dosing rate (max) 1.25 mL/min Dosing rate (min) 100 μL/minTermination At EP Yes Termination delay 5 s At Vmax 10.0 mL Max. time 600 s

Method008 Calculation R1 Result Content Result unit mg/L Formula R1=Q*C/m Constant C=M*1000/z M M[Sulfur dioxide] z z[Sulfur dioxide] Decimal places 3 Result limits No Add. statistics functionalities No


010 End of sample

60

M420

Water, H2OM = 18.01 g/mol, z = 1

50 mL dry methanol

KF one component titrantc = 5 mg H2O/mL

Titration Excellence T50/T70/T90DV705 KF Titration stand

1) SO2 + R1N + R2OH = (R1NH)SO3R2

2) (R1NH)SO3R2 + I2 + H2O + 2 R1N =

(R1NH)SO4R2 + H2SO4 + 2 (R1NH)I

1 DV1005 BuretteXS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

DIspose as organic solvent.Wastedisposal

Preparation and Procedures0.5-1 g ethanolSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Water Content in Ethanol According to Karl Fischer Reaction

1) 50 mL dry methanol are added into the titration cell.

2) The method is started to eliminate all moisture present in thesolvent (pretitration). In this case, no sample is added ("dummysample titration").

2) A drift determination is started (see application M422) andthe drift value is stored as auxiliary value H[KF Drift].

3) A titer determination is performed using di-sodium tartratedihydrate as a primary standard (see application M421).

4) The sample is added with a syringe. The sample size isdetermined by back-weighing.


2) The KF reagent and the solvent must be protected againstintake of air humidity. Drying tubes (ME-23961) filled withmolecular sieve and holders (ME-23915) are used for thispurpose.

Literature:- METTLER TOLEDO Appl. brochure 26, ME-51 709 855.- METTLER TOLEDO Appl. brochure 23, ME-51 725 023- METTLER TOLEDO Appl. brochure 12, ME-51 724 765

Remarks

ConsumptionR1 = VEND; mLTimeR2 = tUSE ; minWater contentR3 = (VEND-C)*c*TITER*100/(m*1000)C = R2*H[KF Drift]/1000 ; %

Calculation

The water content in ethanol is determined by redox titration with one component KF reagent as a titrant. Thetitration is monitored using a Pt double pin electrode DM143 at a fixed polarization current (voltametricindication)

Standard Disodium tartrate dihydrate, 50 mg


61


All results Method-ID M420 Sample Ethanol (1/1) R1 (Consumption) 2.18625 mL R2 (Time) 4.880 min R3 (Content) 1.756 % Sample Ethanol (1/2) R1 (Consumption) 1.89925 mL R2 (Time) 4.130 min R3 (Content) 1.752 % Sample Ethanol (1/3) R1 (Consumption) 2.17125 mL R2 (Time) 5.400 min R3 (Content) 1.757 % Sample Ethanol (1/4) R1 (Consumption) 2.11675 mL R2 (Time) 4.420 min R3 (Content) 1.749 % Sample Ethanol (1/5) R1 (Consumption) 2.01850 mL R2 (Time) 3.720 min R3 (Content) 1.744 % Sample Ethanol (1/6) R1 (Consumption) 2.20400 mL R2 (Time) 4.320 min R3 (Content) 1.755 %


Titration curve

Results

62

Method M420 Water content KF (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M420 Title Water content KF (EP) Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Ethanol Entry type Weight Lower limit 0.5 g Upper limit 1.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C

003 Titration stand (External stand) Type External stand Titration stand External Stand 1


005 Titration (EP) [1]Titrant Titrant One comp. titrant 5 Concentration 5 mol/LSensor Type Polarized Sensor DM143-SC Unit mV Indication Voltametric Ipol 24 μATemperature acquisition Temperature acquisition NoStir Speed 30 %Predispense Mode Volume Volume 1.5 mL Wait time 10 sControl Control User Endpoint type Absolute Tendency Negative Endpoint value 150 mV Control band 5 mV Dosing rate (max) 2 mL/min Dosing rate (min) 150 μL/minTermination At EP Yes Termination delay 10 s At Vmax 10.0 mL Max. time 1200 s

006 Calculation R1 Result Consumption Result unit mL Formula R1=VEND Constant C=1 M M[None] z z[None] Decimal places 5 Result limits No Add. statistics functionalities No

Method007 Calculation R2 Result Time Result unit min Formula R2=tUSE Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Add. statistics functionalities No

008 Calculation R3 Result Content Result unit % Formula R3=(VEND-C)*c*TITER* *100/(m*1000) Constant C=R2*H[KF Drift]/1000 M M[None] z z[None] Decimal places 3 Result limits No Add. statistics functionalities No

009 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t Last titration function V - t Last titration function dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No Condition No

010 End of sample

63

M421


50 mL dry methanol



1) SO2 + R1N + R2OH = (R1NH)SO3R2

2) (R1NH)SO3R2 + I2 + H2O + 2 R1N =



METTLER TOLEDO


Preparation and ProceduresDisodium-tartrate dihydrate,0.03-0.07 g

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Titer of 5 mg H2O/mL Karl Fischer One Component Reagent


2) The general KF method M420 is started to eliminate allmoisture present in the solvent (pretitration). In this case, nosample is added ("dummy sample titration").

3) The method M422 is started and the drift value in μL/min isstored as auxiliary value H[KF Drift].

4) The sample is added with a weighing boat. The sample sizeis determined by back-weighing.

5) It is recommended to replace the solvent after 3 samples, asits dissolving capacity is exhausted.



3) The mean value of the titer is automatically stored as part ofthe setup data by means of the function "Titer".

4) The concentration of the KF titrant must be set to 5 mol/Lsince the concentration can not be defined as mg/mL.

5) If the titer value is lower than 0.8, it is recommended toreplace the titrant with fresh one.


Remarks

ConsumptionR1 = VEND ; mLTimeR2 = tUSE ; minTiterR3 = (15.66*10*m+C)/(VEND/c)C = R2*H[KF Drift]/1000

Calculation

The titer of one component KF reagent is determined by redox titration with disodium tartrate dihydrate. Thetitration is monitored using a Pt double pin electrode DM143 at a fixed polarization current (voltametricindication)

Standard --


64


All results Method-ID M421 Sample Disodium tartrate (1/1) R1 (Consumption) 1.64925 mL R2 (Time) 5.600 min R3 (Titer) 1.023759 Sample Disodium tartrate (1/2) R1 (Consumption) 1.60550 mL R2 (Time) 5.020 min R3 (Titer) 1.032610 Sample Disodium tartrate (1/3) R1 (Consumption) 1.87650 mL R2 (Time) 4.950 min R3 (Titer) 1.024185 Sample Disodium tartrate (1/4) R1 (Consumption) 1.89275 mL R2 (Time) 5.600 min R3 (Titer) 1.028735 Sample Disodium tartrate (1/5) R1 (Consumption) 1.91725 mL R2 (Time) 5.400 min R3 (Titer) 1.028331 Sample Disodium tartrate (1/6) R1 (Consumption) 1.91600 mL R2 (Time) 5.520 min R3 (Titer) 1.029002

Statistics Method-ID M421 R3 Titer Samples 6 Mean 1.027770 s 0.003 srel 0.323 %

Titration curve

Results

65

Method M421 Titer KF (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M421 Title Titer KF (EP) Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample (Titer) Titrant One comp. titrant 5 Concentration 5 mol/L Standard Disodium tartrate Type of standard Solid Entry type Weight Lower limit 0.03 g Upper limit 0.07 g Correction factor 1.0 Temperature 25.0°C Entry Arbitrary



005 Titration (EP) [1]Titrant Titrant One comp. titrant 5 Concentration 5 mol/LSensor Type Polarized Sensor DM143-SC Unit mV Indication Voltametric Ipol 24 μATemperature acquisition Temperature acquisition NoStir Speed 30 %Predispense Mode Volume Volume 0.5 mL Wait time 10 sControl Control User Endpoint type Absolute Tendency Negative Endpoint value 150 mV Control band 5 mV Dosing rate (max) 2 mL/min Dosing rate (min) 150 μL/minTermination At EP Yes Termination delay 10 s At Vmax 10.0 mL Max. time 1200 s

006 Calculation R1 Result Consumption Result unit mL Formula R1=VEND Constant C=1 M M[Disodium tartrate] z z[Disodium tartrate] Decimal places 5 Result limits No Add. statistics functionalities No

Method007 Calculation R2 Result Time Result unit min Formula R2=tUSE Constant C=1 M M[Disodium tartrate] z z[Disodium tartrate] Decimal places 3 Result limits No Add. statistics functionalities No

008 Calculation R3 Result Titer Result unit Formula R3=(15.66*10*m+C)/(VEND/c) Constant C=R2*H[KF Drift]/1000 M M[Disodium tartrate] z z[Disodium tartrate] Decimal places 6 Result limits No Add. statistics functionalities No

009 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t Last titration function V - t Last titration function dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

010 End of sample

011 Titer Titrant One comp. titrant 5 Concentration 5 mol/L Titer= Mean[R3] Result limits No

012 Calculation R4 Result Mean Titer Result unit No Formula R4=Mean[R3] Constant C=1 M M[Disodium tartrate] z z[Disodium tartrate] Decimal places 5 Result limits No Add. statistics functionalities No


66

M422


50 mL dry methanol



1) SO2 + R1N + R2OH = (R1NH)SO3R2

2) (R1NH)SO3R2 + I2 + H2O + 2 R1N =


1 DV1005 BuretteOlivetti JobJet 210 Printer

METTLER TOLEDO


Preparation and Procedures-- Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Drift Determination for The Karl Fischer Titration


2) The general KF method M420 is started to eliminate allmoisture present in the solvent (pretitration). In this case, nosample is added ("dummy sample titration").

3) The method M422 is started and the drift value in μL/min isstored as auxiliary value H[KF Drift].

4) To achieve an accurate drift determination it is recommendedto perform it immediately after pretitration of the solvent, or afterthe standby titration. A series of 2-3 drift determination isrecommended.

1) The method parameters have been optimised for the solventused in this application. Thus, it may be necessary to slightlyadapt the method to your specific solvent or solvent mixture.



Remarks

ConsumptionR1 = VEND *1000; μLTimeR2 = t*60 ; secDriftR3 = 60*R1/R2 ; μg/min

Calculation

The drift of the KF titration vessel is determined by redox titration. The titration is monitored using a Pt doublepin electrode DM143 at a fixed polarization current (voltametric indication)

Standard --


67


All results Method-ID M422 Sample KF Solvent (1/1) R1 (Consumption) 6.250 μL R2 (Time) 604.200 s R3 (Drift KF) 0.625 μL/min Sample KF Solvent (1/2) R1 (Consumption) 6.000 μL R2 (Time) 604.200 s R3 (Drift) 0.600 μL/min Sample KF Solvent (1/3) R1 (Consumption) 5.750 μL R2 (Time) 604.200 s R3 (Drift KF) 0.575 μL/min Sample KF Solvent (1/4) R1 (Consumption) 5.000 μL R2 (Time) 604.200 s R3 (Drift KF) 0.500 μL/min Sample KF Solvent (1/5) R1 (Consumption) 6.750 μL R2 (Time) 604.200 s R3 (Drift) 0.675 μL/min Sample KF Solvent (1/6) R1 (Consumption) 5.250 μL R2 (Time) 604.200 s R3 (Drift KF) 0.525 μL/min

Statistics Method-ID M422 R3 Drift KF Samples 6 Mean 0.583 μL/min s 0.065 μL/min srel 11.066 %

Titration curve

Results

68

Method M423 Drift KF (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M422 Title KF Drift determination Author METTLER TOLEDO Date/Time 02.08.2006 15:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 KF Solvent Entry type Fixed volume Volume 50.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C

003 Titration stand (Auto stand) Type Auto stand Titration stand Auto Stand 1


005 Titration (EP) [1]Titrant Titrant One comp. titrant 5 Concentration 5 mol/LSensor Type Polarized Sensor DM143-SC Unit mV Indication Voltametric Ipol 24 μATemperature acquisition Temperature acquisition NoStir Speed 30 %Predispense Mode None Wait time 0 sControl Control User Endpoint type Absolute Tendency Negative Endpoint value 150 mV Control band 2000 mV Dosing rate (max) 0.002 mL/min Dosing rate (min) 1 μL/minTermination At EP Yes Termination delay 600 s At Vmax 10.0 mL Max. time 600 s

006 Calculation R1 Result Consumption Result unit μL Formula R1=VEND*1000 Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Add. statistics functionalities No

Method007 Calculation R2 Result Time Result unit sec Formula R2=t*60 Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Add. statistics functionalities No

008 Calculation R3 Result Drift Result unit μL/min Formula R3=60*R1/R2 Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Add. statistics functionalities No

009 Auxiliary value Titrant KF Drift Formula H=R3 Result limits No

010 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data Per series E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t Last titration function V - t Last titration function dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

011 End of sample

012 Calculation R4 Result KF Drift Result unit μL/min Formula R4=R3 Constant C=1 M M[None] z z[None] Decimal places 3 Result limits No Add. statistics functionalities No


69

M423


50 mL dry methanol



1) SO2 + R1N + R2OH = (R1NH)SO3R2

2) (R1NH)SO3R2 + I2 + H2O + 2 R1N =



METTLER TOLEDO


Preparation and Procedures-- Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Standby Titration the Karl Fischer Reaction

1) 50 mL dry methanol are added into the titration cell and themethod is started to eliminate all moisture present in the solvent.


Literature:- METTLER TOLEDO Appl. brochure 26, ME-51 709 855- METTLER TOLEDO Appl. brochure 23, ME-51 725 023- METTLER TOLEDO Appl. brochure 12, ME-51 724 765

Remarks

--Calculation

The KF titration vessel is kept anhydrous by continuously titrating the solvent with one component KFreagent. The titration is monitored using a Pt double pin electrode DM143 at a fixed polarization current(voltametric indication)

Standard Disodium tartrate dihydrate, 50 mg


70


------

Titration curve

Results

71

Method M423 Standby KF (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M423 Title Standby KF (EP) Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Standby Entry type Fixed volume Volume 50.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C



005 Titration (EP) [1]Titrant Titrant One comp. titrant 5 Concentration 5 mol/LSensor Type Polarized Sensor DM143-SC Unit mV Indication Voltametric Ipol 24 μATemperature acquisition Temperature acquisition NoStir Speed 30 %Predispense Mode None Wait time 0 sControl Control User Endpoint type Absolute Tendency Negative Endpoint value 150 mV Control band 2000 mV Dosing rate (max) 0.002 mL/min Dosing rate (min) 1 μL/minTermination At EP Yes Termination delay 100000000 s At Vmax 20.0 mL Max. time infinity

005 End of sample

Method

72

M424

"C-C double bonds", expressed as gBr2/100g sample , M=159.81, z=1

50 mL bromine nr. solvent(see Preparation and procedures)

Bromide-bromate solution, Br-/BrO3-

c(Br2) = 0.05 mol/L

Titration Excellence T50/T70/T901 additional dosing unit1 peristaltic pump (waste pump)

BrO3- + 5 Br- + 6 H+ = 3 Br2 + 3 H2O

R1-CH=CH-R2+Br2 = R1-CHBr-CHBr-R2

By maintaining a temperature between 0°C and5°C only the bromine addition reaction takesplace. Substitution and oxidation are avoided.

DV1010 and DV1020 BurettesThermostatable beaker ME-23517DT1000 Temperature sensorXS205 Balance

METTLER TOLEDO

Dispose the waste as halogenatedorganic solvent.

Wastedisposal

Preparation and Procedures0.01-0.6 g petrol;Also for: petroleum distillates andaliphatic alkenes with 1-200g Br2/100g

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Bromine Number in Petrol According to ASTM D1159-01

1) Bromine Nr. solvent preparation:714 mL glacial acetic acid, 134 mL 1,1,1,-trichloroethane, 134mL methanol and 18 mL H2SO4 (16% v/v) are mixed in 1 Lvolumetric flask.

2) A blank value is determined accordind to application M425and stored as blank value B[ASTM D1159]. It is determined forevery new batch of solvent mixture.

3) Titrant preparation:Dissolve 10.2 g KBr and 2.78 g of KBrO3 with deionized waterinto a 1 L volumetric flask and fill up to the mark. The salts aredried at 105°C (220 F) during 30 minutes. The titrant can alsobe bought commercially. The commercially available productcan be used without further standardization.

4) The Br2-number is an indication of the quantity of bromine-reactive constituents. It represents the amount (g) of Br2 whichreacts with 100 g sample under the condition of the standardtest method.

5) The method parameters have been optimised for the sampleused in this application. It may be necessary to slightly adaptthe method to your specific sample. This application does notreplace the ASTM standard.

1) Sample size for bromine number < 50: Direct titrationDepending on the Br2-number, the appropriate amount has to beweighed in (back-weighing) and filled directly into the vesselwith 50 mL of the bromine number solvent.

Bromine Number Sample size/g1 - 5 6.0 - 1.25 - 10 1.0 - 0.610 - 20 0.5 - 0.320 - 50 0.25 - 0.1

2) Sample size for bromine number > 50: Dilution- 10 mL of 1,1,1-trichloroethane are placed in a 50 mL flaskand a test specimen is added as indicated below:

Bromine Number Sample size/g50 - 100 1.0 - 0.6100 - 200 0.5 - 0.4200 - 500 0.35 - 0.15-The sample mass (m') is obtained by back-weighing(accuracy: +/- 1 mg)- Fill the flask to the mark with 1,1,1-trichloroethane and mix.- A 5 mL aliquot of this solution has to be filled into thethermostatable beaker together with 50 mL of the solvent.4- Take care to enter m'/10 as sample mass.

Remarks

Bromine number, g Br2 /100 gR = (QEND-B[ASTM D1159])*C/mC = M/(10*z)

Calculation

Method for the determination of the bromine number in petrol by titration with a bromide-bromate solution.The titration is monitored using a Pt double pin electrode DM143 at a fixed polarization current (voltametricindication)

Standard --


73


All results Method-ID M424 Sample Petrol (1/1) R1 (Bromine number) 19.62059 g/100 g Sample Petrol (1/2) R1 (Bromine number) 19.65058 g/100 g Sample Petrol (1/3) R1 (Bromine number) 19.60262 g/100 g Sample Petrol (1/4) R1 (Bromine number) 19.82843 g/100 g Sample Petrol (1/5) R1 (Bromine number) 19.69236 g/100 g Sample Petrol (1/6) R1 (Bromine number) 19.71195 g/100 g

Statistics Method-ID M424 R1 Bromine number Samples 6 Mean 19.68382 g/100 g s 0.08055 g/100 g srel 0.409 %

Titration curve

Results

74

Method M424 Bromine number ASTM D1159 (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M424 Title Bromine number ASTM D1159 (EP) Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Petrol Entry type Weight Lower limit 0.01 g Upper limit 6.00 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary

003 Titration stand (Manual stand) Type Manual Stand Titration stand Manual Stand 1

004 Dispense (normal) [1] Titrant Bromine nr. solvent Concentration 1 Volume 50.0 mL Dosing rate 60.0 mL/min


006 Titration (EP) [1]Titrant Titrant Bromide-Bromate Concentration 0.05 mol/LSensor Type Polarized Sensor DM143-SC Unit mV Indication Voltametric Ipol 10 μATemperature acquisition Temperature acquisition Yes Temperature sensor DT1000 Unit °CStir Speed 25 %Predispense Mode None Wait time 0 sControl Control Mettler End point type Absolute Tendency Negative End point value 150 mV Control band 0.1 mV Dosing rate (max) 1.0 mL/min Dosing rate (min) 350 μL/minTermination At EP Yes Termination delay 15.0 s At Vmax 10.0 mL Max. time infinity

Method007 Calculation R1 Result Bromine number Result unit g/100 g Formula R=(QEND-B[ASTM D1159])*C/m Constant C=M/(10*z) M M[Bromine] z z[Bromine] Decimal places 5 Result limits No Add. statistics functionalities No

008 Drain Drain pump SP250 Drain volume 80.0 mL

009 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t Last titration function V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No Condition No

010 End of sample

75

M425

"C-C double bonds", expressed as gBr2/100g sample , M=159.81, z=1

--

Bromide-bromate, Br-/BrO3-

c(Br2) = 0.05 mol/L

Titration Excellence T50/T70/T901 additional dosing unit1 peristaltic pump (waste pump)

BrO3- + 5 Br- + 6 H+ = 3 Br2 + 3 H2O

R1-CH=CH-R2+Br2 = R1-CHBr-CHBr-R2

DV1010 and DV1020 BurettesThermostatable beaker ME-23517DT1000 Temperature sensorXS205 Balance

METTLER TOLEDO

Dispose the waste as halogenatedorganic solvent.

Wastedisposal

Preparation and Procedures50 mL bromine nr. solventSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SCIndication

Blank Value for Bromine Number Solvent According to ASTM D1159-01

1) Bromine Nr. solvent preparation:714 mL glacial acetic acid, 134 mL 1,1,1,-trichloroethane, 134mL methanol and 18 mL H2SO4 (16% v/v) are mixed in 1 Lvolumetric flask.

2) Titrant preparation:Dissolve 10.2 g KBr and 2.78 g of KBrO3 with deionized waterinto a 1 L volumetric flask and fill up to the mark. The salts aredried at 105°C (220 F) during 30 minutes. The titrant can alsobe bought commercially. The commercially available productcan be used without further standardization.

3) Determination of blank value:50 mL of bromine nr. solvent are dispensed using an additionaldosing unit. This step can be dispensed manually by using apipette. The titration is started and the titrant consumption inmmol to the endpoint is stored as B[ASTM D1159] by means ofthe method function Blank.

4) With sample having a bromine number smaller than50 g Br2/100g the blank is performed by analysing 50 mL ofsolvent. For blank determination of samples with brominenumber larger than 50 gr Br2/100 g, 5 mL 1,1,1-trichloroethaneare added to 50 mL of the solvent.

1) This application does not replace the ASTM standard.

2) The magnitude of the bromine number is an indication of thequantity of bromine-reactive constituents. It represents theamount (g) of bromine which reacts with 100 g of the sampleunder the condition of the standard test method.

3) By maintaining a temperature between 0°C and 5°C only thebromine addition reaction takes place. Substitution andoxidation are avoided.

4) According to the standard the blank titration of 110 mLsolvent should use less than 0.1 mL of titrant, otherwise thesolvent should be disposed and a fresh batch produced. In thisapplication we have not disposed the solvent to reduce thewaste amount.

Literature:1) ASTM D1159-01, see www.astm.org2) Memory Card Application Package,"Determination in the Petroleum Industry",METTLER TOLEDO Application brochure 20, ME-51 725 020.

Remarks

Blank value for bromine numberR = QEND

R is stored as blank valueB[ASTM D1159].

Calculation

Method for the determination of the blank value of the bromine number solvent by titration with abromide-bromate solution. The titration is monitored using a Pt double pin electrode DM143 at a fixedpolarization current (voltametric indication)

Standard --


76


All results Method-ID M425 Sample Bromine nr. solvent (1/1) R1 (Consumption) 0.01695 mmol Sample Bromine nr. solvent (1/2) R1 (Consumption) 0.01713 mmol Sample Bromine nr. solvent (1/3) R1 (Consumption) 0.01690 mmol Sample Bromine nr. solvent (1/4) R1 (Consumption) 0.01688 mmol Sample Bromine nr. solvent (1/5) R1 (Consumption) 0.01663 mmol Sample Bromine nr. solvent (1/6) R1 (Consumption) 0.01685 mmol

Statistics Method-ID M425 R1 Bromine nr. solvent Samples 6 Mean 0.01689 mmol s 0.00016 mmol srel 0.958 %

Titration curve

Results

77

Method M425 Blank ASTM D1159 (EP) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M425 Title Blank ASTM D1159 (EP) Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Bromine nr. solvent Entry type Fixed volume Volume 50.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C


004 Dispense (normal) [1] Titrant Bromine nr. solvent Concentration 1 Volume 50.0 mL Dosing rate 60.0 mL/min


006 Titration (EP) [1]Titrant Titrant Bromide-Bromate Concentration 0.05 mol/LSensor Parameters Type Polarized Sensor DM143 Unit mV Indication Voltametric Ipol 10 μATemperature acquisition Temperature acquisition Yes Temperature sensor DT1000 Unit °CStir Speed 25 %Predispense Mode None Wait time 0 sControl Control User Endpoint type Absolute Tendency Negative Endpoint value 150 mV Control band 0.1 mV Dosing rate (max) 1.0 mL/min Dosing rate (min) 350 μL/minTermination At EP Yes Termination delay 15.0 s At Vmax 10.0 mL Max. time infinity

Method007 Calculation R1 Result Consumption Result unit mmol Formula R=QEND Constant C=1 M M[None] z z[None] Decimal places 5 Result limits No Add. statistics functionalities No

008 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t Last titration function V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No Condition No

009 Drain Drain pump SP250 Drain volume 80.0 mL

010 End of sample

011 Blank Name ASTM D1159 Formula B=Mean[R1] Unit mmol Limits No

012 Calculation R2 Result Mean consumption Result unit mmol Formula R2=Mean[R1] Constant C=1 M M[None] z z[None] Decimal places 5 Result limits No Add. statistics functionalities No013 Record Results Yes Raw results No Resource data No Calibration curve No Method No Series data No

78

M426

Acid components as mg KOH/gsample, M=56.1 g/mol, z=1

60 mL ASTM D664-04 solvent:Toluene:2-propanol:deion. water500 mL : 495 mL : 5 mL

Potassium hydroxide in 2-PropanolKOH, c(KOH) = 0.1 mol/L


KOH + HA = KA + H2O

HA: Acid components

DV1010 BuretteTitration glass beaker ME-101446XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Dispose as aromatic organic solvent(toluene)

Wastedisposal

Preparation and ProceduresMotor oil, approx. 5 g for AN 1-5Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Acid Number in Motor Oil According to ASTM D664-04

1) The titer is determined using potassium hydrogen phthalate(KHP): add approx. 80 mg KHP into a glass titration beakerand dissolve it with 60 mL deion. water.

2) The buffer potential 1 (pH 4) and the buffer potential 2(pH 11) are determined using aqueous pH buffers. Thesevalues are stored as auxiliary values H{Buffer pH4] andH[Buffer pH11].

3) A blank value is determined for every new batch of solventmixture (see M427) and stored as B[ASTM664].

4) Depending on the AN of the sample, different sampleamounts are requested:AN0.05 - <1.0 20.0 +/- 2.01.0 - <5.0 5.0 +/- 0.55 - <20 1.0 +/- 0.120 - <100 0.25 +/- 0.02100 - <260 0.1 +/- 0.01

5) After each sample titration the DG113-SC sensor has to berinsed and conditioned in deion. water during 5 minutes.Subsequently, the electrode is rinsed with solvent before startingnext titration.



3) The acid number indicates the amount of base as mg KOH/gsample needed to titrate the acidic constituents in a sampleunder specific conditions, i.e. specified solvent and endpoint.

4) The sample is titrated using an EQP method function. If noinflection point is detected, endpoints are taken at meterreadings corresponding to those found for aqueous acidic andbasic buffer solutions i.e. pH 4 and 11:4.1. Acidic buffer pH 4 :Strong Acid Number (SAN), titration with HCl in 2-propanol4.2. Basic buffer pH 11:Acid Number (AN), titration with KOH in 2-Propanol

5) In this application the SAN at pH 4 could not be calculatedsince the initial potential was already below buffer potential 1(pH 4).

Literature:- ASTM D664-04, see www.astm.org- METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Remarks

R1=(Q-B[ASTM664])*C/m, C=MAN (mg KOH/g) at EQP

R2=QE(H[pH11]-B[ASTM664])*C/m,C=MKOH cons. (mmol) at buffer pot. 2

Calculation

Method for the determination of the acid number (AN) in motor oil by potentiometric titration with potassiumhydroxide in 2-propanol.


Thomas HitzAuthor

79


All results Method-ID M426 Sample Motor oil (1/1) R1 (Content) 2.053 mg KOH/g R2 (Content) 2.177 mg KOH/g Sample Motor oil (1/2) R1 (Content) 2.075 mg KOH/g R2 (Content) 2.247 mg KOH/g Sample Motor oil (1/3) R1 (Content) ----- mg KOH/g R2 (Content) 2.262 mg KOH/g Sample Motor oil (1/4) R1 (Content) ----- mg KOH/g R2 (Content) 2.262 mg KOH/g Sample Motor oil (1/5) R1 (Content) ----- mg KOH/g R2 (Content) 0.294 mg KOH/g Sample Motor oil (1/6) R1 (Content) 2.147 mg KOH/g R2 (Content) 2.471 mg KOH/g

Statistics Method-ID M426 R1 Content Samples 3 Mean 2.092 mg KOH/g s 0.040 mg KOH/g srel 1.919 % R2 Content Samples 6 Mean 2.286 mg KOH/g s 0.090 mg KOH/g srel 3.947 %

Titration curve

Results

80

Method M426 Acid number ASTM D664 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M426 Title Acid number ASTM D664 Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Motor oil Entry type Weight Lower limit 0.0 g Upper limit 10.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary



005 Titration (EQP) [1] Titrant Titrant KOH in 2-Propanol Concentration 0.1 mol/LSensor Type pH Sensor DG113-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35 %Predispense Mode None Wait time 0 sControl Control User Titrant addition Dynamic dE(set value) 15.0 mV dV(min) 0.01 mL dV(max) 0.5 mL Meas. value acquisition Equilibrium controlled dE 1.0 mV dt 1 s t(min) 5 s t(max) 40 sEvaluation and recognition Procedure Standard Threshold 50 mV/mL Tendency Negative Ranges 1 Lower limit - 300 mV Upper limit 50 mV Add. EQP criteria NoTermination At Vmax 10.0 mL At potential Yes Potential - 240 Termination tendency None At slope No After number of recognized EQPs No Number of EQPs No Combined termination criteria No

Method006 Calculation R1 Result Content Result unit mg KOH/g Formula R1=(Q-B[ASTM664])*C/m Constant C=M/z M M[Potassium hydroxide] z z[Potassium hydroxide] Decimal places 3 Result limits No Add. statistics functionalities No

007 Calculation R2 Result Content Result unit mmol Formula R2=(QE(H[Buffer pH11]- B[ASTM664])*C/m Constant C=M M M[KOH] z z[KOH] Decimal places 3 Result limits No Add. statistics functionalities No


009 End of sample

81

M427

Acid components as mg KOH/gsample, M=56.1 g/mol, z=1

--

Potassium hydroxide in 2-PropanolKOH, c(KOH) = 0.1 mol/L


KOH + HA = KA + H2O

HA: Acid components

1 DV1010 BuretteTitration glass beaker ME-101446XS205 BalanceOlivetti JobJet 210 Printer

METTLER TOLEDO

Dispose as aromatic organic solvent(toluene)

Wastedisposal

Preparation and Procedures60 mL ASTM D664-04 solvent:Toluene:2-propanol: deion. water500 mL : 495 mL : 5 mL

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Blank Value of Acid Number Solvent According to ASTM D664-04

1) The titer is determined using potassium hydrogen phthalate(KHP): add approx. 80 mg KHP into a glass titration beakerand dissolve it with 60 mL deionized water.

2) The buffer potential 1 (pH 4) and the buffer potential 2(pH 11) are determined using aqueous pH buffers. Thesevalues are stored as H{Buffer pH4] and H[Buffer pH11].

3) Since no inflection point was detected, the endpoint potentialwas determined using buffer pH 11 (evaluation at pH 11).

4) After each sample the electrode was cleaned with 2-propanoland conditioned for 300 s in deionized water. The potential atpH 11.0 was determined again and compared with the initialpotential (first determination). If the potential difference was lessor equal 2 mV, then the next sample for blank determinationwas started.



3) The acid number indicates the amount of base as mg KOH/gsample needed to titrate the acidic constituents in a sampleunder specific conditions, i.e. specified solvent and endpoint.

4) The sample is titrated using an EQP method function. If noinflection point is detected, endpoints are taken at meterreadings corresponding to those found for aqueous acidic andbasic buffer solutions i.e. pH 4 and 11:4.1. Acidic buffer pH 4 :Strong Acid Number (SAN), titration with HCl in 2-propanol4.2. Basic buffer pH 11:Acid Number (AN), titration with KOH in 2-Propanol

Literature:- ASTM D664-04, see www.astm.org- METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Remarks

R1 = Q ; mmolR2 = QE(H[pH11]) ; mmol

Calculation

Method for the blank value determination of the acid number (AN) solvent by potentiometric titration withpotassium hydroxide in 2-propanol in non aqueous solvent according to ASTM D664-04


Thomas HitzAuthor

82


All results Method-ID M427 Sample Blank ASTM D664 (EP) (1/1) R1 (Consumption) 0.00570 mmol Sample Blank ASTM D664 (EP) (1/2) R1 (Consumption) 0.00550 mmol Sample Blank ASTM D664 (EP) (1/3) R1 (Consumption) 0.00560 mmol Sample Blank ASTM D664 (EP) (1/4) R1 (Consumption) 0.00530 mmol Sample Blank ASTM D664 (EP) (1/5) R1 (Consumption) 0.00550 mmol Sample Blank ASTM D664 (EP) (1/6) R1 (Consumption) 0.00560 mmol


Titration curve

Results

83

Method M427 Blank ASTM D664 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M427 Title Blank ASTM D664 Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Solvent ASTM D664 Entry type Fixed volume Volume 60.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C



005 Titration (EP) [1]Titrant Titrant KOH in 2-Propanol Concentration 0.1 mol/LSensor Parameters Type pH Sensor DG113-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35 %Predispense Mode None Wait time 0 sControl Control User Endpoint type Absolute Tendency Negative Endpoint value H[Buffer pH11] mV Control band 300 mV Dosing rate (max) 0.1 mL/min Dosing rate (min) 10 μL/minTermination At EP Yes Termination delay 0 s At Vmax 2.0 mL Max. time infinity

006 Calculation R1 Result Consumption Result unit mmol Formula R1=Q Constant C=1 M M[None] z z[None] Decimal places 5 Result limits No Add. statistics functionalities No

Method007 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V No E - t Last titration function V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

008 End of sample

009 Blank Name ASTM664 Value B=Mean[R1] Units mmol Limits No

010 Calculation R2 Result Mean consumption Result unit mmol Formula R2=Mean[R1] Constant C=1 M M[None] z z[None] Decimal places 5 Result limits No Add. statistics functionalities No


84

M428

Alkaline components in oil expressedas KOH, M=56.1 g/mol , z=1

60 mL ASTM D4739-05 solvent(see Preparation and Procedures)

HCl in 2-propanol, c(HCl)=0.1 mol/LKOH in 2-propanol, c(HCl)=0.1 mol/L

Titration Excellence T50/T70/T90Rondo 60 Sample changer1 additional dosing unit (20 mL)

HCl + NaOH = Cl- + Na+ + H2O

NaOH represents the alkalinecomponents.

DV1010 and DV1020 BurettesGlass beaker ME-101446XS205 Balance, SP250Olivetti Printer JobJet 210

METTLER TOLEDO

Disposal as halogenated organic wasteWastedisposal

Preparation and ProceduresCutting oil, 0.1-10 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Base Number According to ASTM D4739-05

1) Solvent preparation:ASTM D4739-05 solvent is prepared by mixing 2-propanol,toluene, chloroform and water in the following ratio:10 : 10 : 10 : 0.3 (v/v).

2) The titer is determined by titration of standardized KOH in2-propanol solution. The latter is standardized using potassiumhydrogen phthalate (KHP).

3) The acidic and the alkaline aqueous buffers are measuredand stored as auxiliary values pH3 (BN) and pH10 (SBN).

4) Blank value determinations for the base number aredetermined for every new batch of solvent mixture by titrationwith HCl in 2-propanol to pH 3 buffer potential value (M429).The result is stored as blank value B[ASTM D4739]. For SBN,the solvent is titrated with KOH in 2-propanol to pH 10 pot.value.

5) Add the oil sample into the titration beaker. The appropriatesample size is calculated according to the following formula:sample size (g) = 7/expected BN

6) 60 mL ASTM D4739-05 solvent are added using anadditional dosing unit. This step can be performed manuallyusing a dispenser or a graduated cylinder.

This method allows a fully automated procedure using asample changer and an additional dosing unit. It can bemodified for manual operation. Select "Manual stand" in themethod function "Titration stand".

1) This application does not replace the ASTM standard.The method parameters have been optimised for the sampleused in this application. Thus, it may be necessary to slightlyadapt the method to your specific sample.

2) The base number BN is defined as the consumption ofhydrochloric acid to a specific endpoint to neutralize the alkalinecomponents of the oil. It is expressed as mg KOH/g sample:- If an EQP is found between the acidic buffer potential value anda point 100 mV past this potential, then this will be the BN.- If no EQP is found in this region, then the result is evaluated athe potential value of the acidic buffer.

3) Between each sample it is necessary to condition theelectrode under stirring during 300 s in deion. water. Theelectrode is parked in buffer pH 4 (Rinse beaker).Literature:1) ASTM D4739-05 and 4739-04 Draft , see www.astm.org2) METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Remarks

Base number mg KOH/g:R1=(Q-B[ASTM D4739])*C/m, C=M/z

Base number mg KOH/g at acidic potential:R2=(QE(H[Buffer pH3])-B[ASTM D4739])*C/m;C=M/z

Calculation

Method for the determination of the base number BN in oil by titration with hydrochloric acid in 2-propanolaccording to ASTM D4739-05.

Standard KOH in 2-propanol 0.1 mol/L / KHP


85


All results Method-ID M428 Sample Cutting oil (1/1) R1 (Content) 19.48 mg KOH/g R2 (Content) 17.15 mg KOH/g Sample Cutting oil (1/2) R1 (Content) 19.70 mg KOH/g R2 (Content) 15.33 mg KOH/g Sample Cutting oil (1/3) R1 (Content) 19.84 mg KOH/g R2 (Content) 15.38 mg KOH/g Sample Cutting oil (1/4) R1 (Content) 19.15 mg KOH/g R2 (Content) 15.91 mg KOH/g Sample Cutting oil (1/5) R1 (Content) 19.34 mg KOH/g R2 (Content) 15.86 mg KOH/g

Statistics Method-ID M428 R1 Cutting oil Samples 5 Mean 19.50 mg KOH/g s 0.27 mg KOH/g srel 1.404 % R2 Cutting oil Samples 5 Mean 15.93 mg KOH/g s 0.74 mg KOH/g srel 4.620 %

Titration curve

Results

86

Method M428 Base number ASTM D4739 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M428 Title Base number ASTM D4739 Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Cutting oil Entry type Weight Lower limit 0.0 g Upper limit 10.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary

003 Titration stand (Rondo60/TowerA) Type Rondo60/TowerA Titration stand Rondo60/1A

004 Dispense (normal)[1] Titrant ASTM D4739 solvent Concentration 1 Volume 60.0 mL Dosing rate 60.0 mL/min


006 Titration (EQP) [1]Titrant Titrant HCl in 2-Propanol Concentration 0.1 mol/LSensor Type pH Sensor DG113-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode Volume Volume 0.5 mL Wait time 30 sControl Control User Titrant addition Incremental dV 0.1 mL Meas. val. acquisition Fixed time dt 90.0 sEvaluation and Recognition Procedure Standard Threshold 5 mV/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 3.0 mL At potential No At slope No After number of recognized EQPs No Combined termination criteria No

007 Calculation R1Result ContentResult unit mg KOH/gFormula R1=(Q-B[ASTM D4739])*C/mConstant C=M/zM M[Potassium hydroxide]z z[Potassium hydroxide]Decimal places 2Result limits No

Add. statistics functionalities No

Method008 Calculation R2 Result Content Result unit mg KOH/g Formula R2=(QE(H[Buffer pH3]- B[ASTM D4739])*C/m Constant C=M/z M M[Potassium hydroxide] z z[Potassium hydroxide] Decimal places 2 Result limits No Add. statistics functionalities No

009 Rinse Auxiliary reagent ASTM D4739 Rinse cycles 3 Vol. per cycle 20 mL Position Actual position Drain Yes Drain pump SP250

010 Conditioning Typ Fix Interval 1 Position Conditioning Time [s] 300 s Speed [%] 30%


012 End of sample

013 Park Titration Stand Rondo60/1A Position Rinse beaker

87

M429

--

--

HCl in 2-propanol, c(HCl)=0.1 mol/LKOH in 2-propanol, c(HCl)=0.1 mol/L

Titration Excellence T50/T70/T90Rondo 60 Sample changer1 additional dosing unit (20 mL)

--

DV1010 and DV1020 BurettesGlass beaker ME-101446XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO


Preparation and Procedures60 mL solvent ASTM D4739-05Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Blank Value of Base Number Solvent According to ASTM D4739-05

1) Solvent preparation:ASTM D4739-05 solvent is prepared by mixing 2-propanol,toluene, chloroform and water in the following ratio:10 : 10 : 10 : 0.3 (v/v).

2) The titer is determined by titration of standardized KOH in2-propanol solution. The latter is standardized using potassiumhydrogen phthalate (KHP).

3) The acidic and the alkaline aqueous buffers are measuredand stored as auxiliary values H[pH3] (BN) and H[pH10](SBN, Strong Base Number). The values are then used in theparameter "Termination at potential" of the method function"Titration EQP".

4) 60 mL ASTM D4739-05 solvent are added using anadditional dosing unit. This step can be performed manuallyusing a dispenser or a graduated cylinder.

5) Blank value determinations are determined for every newbatch of solvent by titration with HCl in 2-propanol to pH 3potential value. The result is stored as blank B[ASTM D4739].

6) For SBN, the solvent is titrated with KOH in 2-propanol to pH10 buffer potential value and stored as B[ASTM D4739 pH10].

This method allows a fully automated procedure using a samplechanger and an additional dosing unit. It can be modified formanual operation. Select "Manual stand" in the method function"Titration stand".


2) The base number BN is defined as the consumption ofhydrochloric acid to a specific endpoint to neutralize the alkalinecomponents of the oil. It is expressed as mg KOH/g sample:- If an EQP is found between the acidic buffer potential value anda point 100 mV past this potential, then this will be the BN.- If no EQP is found in this region, then the result is evaluated athe potential value of the acidic buffer.

3) Between each sample it is necessary to condition theelectrode under stirring during 300 s in deion. water. Theelectrode is subsequently cleaned in a beaker containingsolvent.

Literature:1) ASTM D4739-05 and 4739-04 Draft , see www.astm.org2) METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Remarks

BN blank: Consumption of HCl/ 2Propanolup to acidic potential value:R1=QEND, mmol

SBN blank: Consumption of KOH/2-Prop. upto alkaline potential value:R1=QEND, mmol

Calculation

Blank value determination of the base number BN solvent by titration with hydrochloric acid and potassiumhydroxide in 2-propanol according to ASTM D4739-05.

Standard KOH in 2-propanol 0.1 mol/L / KHP


88


All results Method-ID M429 Sample ASTM D4739 solvent (1/1) R1 (Consumption) 0.00199 mmol Sample ASTM D4739 solvent (1/2) R1 (Consumption) 0.00186 mmol Sample ASTM D4739 solvent (1/3) R1 (Consumption) 0.00193 mmol Sample ASTM D4739 solvent (1/4) R1 (Consumption) 0.00170 mmol Sample ASTM D4739 solvent (1/5) R1 (Consumption) 0.00195 mmol

Statistics Method-ID M429 R1 ASTM D4739 solvent Samples 5 Mean 0.00189 mmol s 0.00111 mmol srel 6.301 %

Titration curve

Results

89

Method M429 Blank BN ASTM D4739 02.08.2006Author METTLER TOLEDO


002 Sample Number of IDs 1 ID 1 ASTM D4739 solvent Entry type Fixed volume Volume 60.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C

003 Titration stand (Rondo60/TowerA) Type Rondo60/TowerA Titration stand Rondo60/Tower1A

004 Dispense (normal) [1] Titrant Solvent ASTM D4739 Concentration 1 mol/L Volume 60.0 mL Dosing rate 60.0 mL/min


006 Titration (EQP) [1]Titrant Titrant HCl in 2-Propanol Concentration 0.1 mol/LSensor Type pH Sensor DG113-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 30%Predispense Mode None Wait time 0 sControl Control User Titrant addition Dynamic dE(set value) 2.0 mV dV(min) 0.002 mL dV(max) 0.05 mL Meas. val. acquisition Fixed time dt 90.0 sEvaluation and Recognition Procedure Standard Threshold 10000 mV/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 1.0 mL At potential Yes Potential 228.6 mV At slope No After number of recognized EQPs No Combined termination criteria No

007 Calculation R1 Result Consummption Result unit mmol Formula R1=QEND Constant C=1 M M[None] z z[None] Decimal places 5 Result limits No Add. statistics functionalities No

Method008 Record

Results Per seriesRaw results Per seriesTable of measured values Last titration functionSample data Per seriesResource data NoE - V Last titration functiondE/dV - V Last titration functionlog dE/dV - V Nod2E/dV2 - V NoE - t NoV - t NodV/dt - t NoT - t NoE - V & dE/dV - V NoV - t & dV/dt - t NoCalibration curve NoMethod NoSeries data No

009 End of sample

010 Park Titration Stand Rondo60/1A Position Rinse beaker (pH 4)

011 Blank Name ASTM D4739 Value B=Mean[R1] Units mmol Limits No



Acidic buffer potential value: 228.6 mV

----------------------------------------------

Strong Base Number, SBN....Titrant Titrant KOH in 2-Propanol Concentration 0.1 mol/L....Evaluation and Recognition Procedure Standard Threshold 10000 mV/mL Tendency Negative Ranges 0 Add. EQP criteria NoTermination At Vmax 1.0 mL At potential Yes Potential - 185.1 mV At slope No

Alkaline buffer potential value: -185.1 mV

90

M430

Alkaline components in oil, expressedas mg KOH/g sample, M=56.1, z=1

60 mL ASTM D2896-05 solvent(see Preparation and Procedures)

Perchloric acid in acetic acid, HClO4

c(HClO4) = 0.1 mol/L

Titration Excellence T50/T70/T901 additional dosing unit (20 mL)

HClO4 + NaOH = ClO4- + Na+ + H2O



METTLER TOLEDO


Preparation and ProceduresCutting oil, 0.5 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SC with saturated NaClO4 inacetic acid as electrolyte

Indication

Base Number in Cutting Oil According to ASTM D2896-05

1) Solvent preparation:ASTM D2896-05 solvent is prepared by mixing one volume partof glacial acetic acid with two volume parts of chlorobenzene(acetic acid:chlorobenzene 1:2 v/v)

2) The titer is determined by titrating potassiumhydrogenphthalate (KHP) as a primary standard: approx. 80mg are dissolved in deonized water in a titration beaker.

3) A blank value is determined for every new batch of solventmixture (see application M431) and stored as blank valueB[ASTM D2896].

4) The appropriate sample size for 60 mL solvent is calculatedaccorrding to the following formula:

Sample size (g) = 10/expected BN

5) The sample is titrated with perchloric acid in acetic acidusing an EQP titration method.

6) 60 mL ASTM D2896-05 solvent are added using anadditional dosing unit. It can be performed manually using apipette.




4) The base number is defined as the consumption of perchloricacid to the first equivalence point for one g of sample in order toneutralize the alkaline components of the oil. It is expressed asmg KOH/g sample.


Remarks

Base number (mg KOH/g)

R = (Q-B[ASTM D2896])*C/m,C = 56.1

Calculation

Method for the determination of the base number BN in cutting oil by titration with perchloric acid solution innon aqueous solvent according to ASTM D2896-05.



91


All results Method-ID M430 Sample Cutting oil (1/1) R1 (Content) 20.24 mg KOH/g Sample Cutting oil (1/2) R1 (Content) 20.31 mg KOH/g Sample Cutting oil (1/3) R1 (Content) 20.14 mg KOH/g Sample Cutting oil (1/4) R1 (Content) 20.36 mg KOH/g Sample Cutting oil (1/5) R1 (Content) 20.15 mg KOH/g Sample Cutting oil (1/6) R1 (Content) 20.16 mg KOH/g

Statistics Method-ID M430 R1 Cutting oil Samples 6 Mean 20.23 mg KOH/g s 0.09 mg KOH/g srel 0.458 %

--------------------------------------------------------------

Results with fixed titrant increments:

Statistics Method-ID INC / BN oil ASTM 2896 R1 Oil Samples 6 Mean 20.372 mg KOH/g s 0.166 mg KOH/g srel 0.814 %

Titration curve

Results

92

Method M430 Base number ASTM D2896 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M430 Title Base number ASTM D2896 Author METTLER TOLEDO Date/Time 02.08.2006 Modified -- Modified by -- Protect SOP None

002 Sample Number of IDs 1 ID 1 Cutting oil Entry type Weight Lower limit 0.1 g Upper limit 10.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary


004 Dispense (normal) [1] Titrant ASTM 2896 solvent Concentration 1 Volume 60.0 mL Dosing rate 60.0 mL/min


006 Titration (EQP) [1]Titrant Titrant HClO4

Concentration 0.1 mol/LSensor Type pH Sensor DG113-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 40%Predispense Mode Volume Volume 0.5 mL Wait time 15 sControl Control User Titrant addition Dynamic dE(set value) 15 mV dV(min) 0.01 mL dV(max) 0.2 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 1 s t(min) 3 s t(max) 30 sEvaluation and Recognition Procedure Standard Threshold 200 mV/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential Yes Potential 850 mV Termination tendency None At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method007 Calculation Result Content Result unit mg KOH/g Formula R=(Q-B[ASTM D2896])*C/m Constant C=56.1 M M[None] z z[None] Decimal places 2 Result limits No Add. statistics functionalities No

008 RecordResults Per seriesRaw results Per seriesTable of measured values Last titration functionSample data Per seriesResource data NoE - V Last titration functiondE/dV - V Last titration functionlog dE/dV - V Nod2E/dV2 - V NoE - t NoV - t NodV/dt - t NoT - t NoE - V & dE/dV - V NoV - t & dV/dt - t NoCalibration curve NoMethod NoSeries data NoCondition No

009 End of sample

-----------------------------------------------

Additional test: fixed titrant increments / fixed time

Control Control Mettler Show parameters Yes Titrant addition Incremental dV 0.05 mL Meas. val. acquisition Fixed time dt 7.0 s

93

M431

Alkaline components, expressed asmmol HClO4 consumption

--

Perchloric acid in acetic acid, HClO4

c(HClO4) = 0.1 mol/L


HClO4 + NaOH = ClO4- + Na+ + H2O



METTLER TOLEDO


Preparation and Procedures60 mL solvent ASTM D2896-05 Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SC with saturated NaClO4 inacetic acid as electrolyte

Indication

Blank Value of Base Number Solvent According to ASTM D2896-05

1) Solvent preparation:ASTM D12896-05 solvent is a prepared by mixing one volumepart of glacial acetic acid with two volume parts ofchlorobenzene (acetic acid:chlorobenzene 1:2 v/v)

2) 60 mL ASTM D2896-05 solvent are added using anadditional dosing unit. It can be performed manually using apipette

3) The sample is titrated with perchloric acid in acetic acidusing an EQP titration method.

4) A blank value is determined for every new batch of solventmixture and stored as blank value B[ASTM D2896].




Remarks

Blank value (mmol):

R = Q, mmolC = 1

Calculation

Method for the determination of the blank value of the base number solvent by titration with perchloric acidsolution in non aqueous solvent according to ASTM D2896-05.



94


All results Method-ID M431 Sample ASTM D2896 solvent (1/1) R1 (Consumption) 0.0006 mmol Sample ASTM D2896 solvent (1/2) R1 (Consumption) 0.0006 mmol Sample ASTM D2896 solvent (1/3) R1 (Consumption) 0.0004 mmol Sample ASTM D2896 solvent (1/4) R1 (Consumption) 0.0005 mmol Sample ASTM D2896 solvent (1/5) R1 (Consumption) 0.0005 mmol Sample ASTM D2896 solvent (1/6) (-) R1 (Consumption) 0.0010 mmol Sample ASTM D2896 solvent (1/7) R1 (Consumption) 0.0005 mmol

Statistics Method-ID M431 R1 Consumption Samples 6 Mean 0.0005 mmol (*) s 0.0001 mmol (*) srel 14.570 %

Sample 1/6 deleted

Titration curve

Results

95

Method M431 Blank ASTM D2896 02.08.2006Author METTLER TOLEDO


002 Sample Number of IDs 1 ID 1 ASTM D2896 solvent Entry type Fixed volume Volume 60.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C


004 Dispense Titrant ASTM D2896 solvent Concentration 1 Volume 60.0 mL Dosing rate 60.0 mL/min


006 Titration (EQP) [1]Titrant Titrant HClO4

Concentration 0.1 mol/LSensor Type pH Sensor DG113-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode None Wait time 0 sControl Control Mettler Show parameters Yes Titrant addition Incremental dV 0.001 mL Meas. val. acquisition Fixed time dt 7 sEvaluation and Recognition Procedure Standard Threshold 500 mV/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 2.0 mL At potential Yes Potential 850 mV Termination tendency None At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method007 Calculation R1 Result Consumption Result unit mmol Formula R1=Q Constant C=1 M M[None] z z[None] Decimal places 4 Result limits No Add. statistics functionalities No

008 End of sample

009 Blank Name ASTM D2896 Value B=Mean[R1] Unit mmol Limits No



96

M432

Chloride, Cl-,M = 35.45 g/mol, z = 1

40 mL solvent ASTM D3227-04a20 mL NaCl in 2-propanol solution(see remarks)

Silver nitrate, AgNO3 , in 2-Propanolc(AgNO3) = 0.01 mol/L

Titration Excellence T50/T70/T902 additional dosing units (10 and 20 mL)Rondolino Sample Changer

NaCl + AgNO3 = AgCl + NaNO3

2 DV1010 and 1 DV1020 BurettesGlass titration beaker ME-101446XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Filtration. The precipitate (AgCl) has tobe classified as special waste. Theliquid phase has to be disposed asaqueous waste.

Wastedisposal

Preparation and ProceduresMotor oil, approx. 0.6 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM141-SCIndication

Chloride Content in Motor Oil

1) A sodium chloride standard solution is used for the titerdetermination. Since small amounts of salt cannot be weighedin exactly, it is recommended to prepare an aqueous solution ofNaCl, and then add the standard with a pipette.

2) Before sample determination a blank value titration of thesolvent spiked with a NaCl standard solution (see 4). The resultis taken into account as B[Chloride ASTM D3227].

3) 0.6 g of sample is added into the titration beaker.

4) 20 mL approx. 50 mg/L NaCl standard solution are added tospike the sample since the chloride content is too low. This stephas been performed using an additional dosing unit. It can beperformed manually using a pipette.

5) Add 40 mL solvent ASTM D3227-04a. This step has beenperformed using an additional dosing unit. It can be performedmanually using a pipette.

6) The sample series were analysed using a Rondolino samplechanger. The conditioning time was set to 30 s (Rondolinosettings: 4). In this way, the electrode was condiitoned in thesample solvent before starting the next titration.

1) The method parameters have been developed and optimisedfor the above mentioned sample. It may be necessary to slightlyadapt the method to your specific sample.

2) A fully automated analysis procedure is performed by usingtwo additional burette drives and a sample changer. The methodcan be easily modified for manual operation. Select "Manualstand" in the method function "Titration stand".

3) ASTM D3227-04a alkaline solvent:Dissolve 1.6 g anhydrous sodium acetate (NaC2H3O2) in 25 mLof deion. water and pour into 1 L flask. Fill up to the mark with2-propanol. This solvent allows a good dissolution of the oil.

4) The NaCl standard solution is prepared by dissolving approx.50 mg NaCl in few mL water, adding it into a 1 L volumetricflask, and then by filling up with the ASTM D3227 solvent.

5) Sulfides interfere with the analysis. If necessary, they have tobe oxidised to sulfates by adding 10 mL 30% H2O2 previous tothe analysis. In this application, this was not the case.

Literature:1) METTLER TOLEDO Application brochure 20, ME-51 725 020.2) ASTM D3227-04a, D4929-04, see www.astm.org

Remarks

R1: Content (ppm)

R1 = (Q-B[Chloride ASTM D3227])*C/m,C = M*1000/z

Calculation

Inorganic chloride content in fresh motor oil is determined by precipitation titration in non aqueous solventwith silver nitrate. The content is expressed as chloride, Cl-.

Standard NaCl, c(NaCl) = 0.01 M , 5 mL


97


All results Method-ID M432 Sample Motor oil (1/1) R1 (Content) 675.23 ppm Sample Motor oil (1/2) R1 (Content) 666.66 ppm Sample Motor oil (1/3) R1 (Content) 676.89 ppm Sample Motor oil (1/4) R1 (Content) 681.68 ppm Sample Motor oil (1/5) R1 (Content) 682.10 ppm Sample Motor oil (1/6) R1 (Content) 885.16 ppm

Statistics Method-ID M432 R1 Content Samples 6 Mean 677.95 ppm s 6.62 ppm srel 0.977 %

Titration curve

Results

98

Method M432 Chloride content in motor oil 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M432 Title Chloride in motor oil Author METTLER TOLEDO Date/Time 02.08.2006 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Motor oil Entry type Weight Lower limit 0.5 g Upper limit 0.7 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary


004 Dispense (normal) [1] Titrant NaCl standard Concentration 0.00009 Volume 20.0 mL Dosing rate 60.0 mL/min

005 Dispense (normal) [2] Titrant ASTM D3227 solvent Concentration 1 Volume 40.0 mL Dosing rate 60.0 mL/min


007 Titration (EQP) [1]Titrant Titrant AgNO3

Concentration 0.01 mol/LSensor Type mV Sensor DM141-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 40%Predispense Mode Volume Potential 1.5 ml Wait time 15 sControl Control Mettler Titrant addition Incremental dV 0.1 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 3 s t(min) 5 s t(max) 15 sEvaluation and Recognition Procedure Standard Threshold 30 mV/mL Tendency Positive Ranges 1 Lower limit 1 -50 mV Upper limit 500 mV Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method008 Calculation R1 Result Content Result unit ppm Formula R=(Q-B[Chloride ASTMD3227])* *C/m Constant C=M*1000/z M M[Chloride] z z[Chloride] Decimal places 2 Result limits No Add. statistics functionalities No

009 RecordResults Per seriesRaw results Per seriesTable of measured values Last titration functionSample data Per seriesResource data NoE - V Last titration functiondE/dV - V Last titration functionlog dE/dV - V Nod2E/dV2 - V NoE - t NoV - t NodV/dt - t NoT - t NoE - V & dE/dV - V NoV - t & dV/dt - t NoCalibration curve NoMethod NoSeries data No

010 End of sample

99

M433

Mercaptan sulfur, R-S-,M = 32.06 g/mol, z = 1

20 mL solvent ASTM D3227-04a2 mL Ethyl mercaptan standard sol.(see remarks)

Silver nitrate, AgNO3 , in 2-Propanolc(AgNO3) = 0.01 mol/L

Titration Excellence T50/T70/T902 additional dosing units (10+20 mL)Rondolino Sample Changer

R-SH + AgNO3 = R-S-Ag + HNO3

2 DV1010 and 1 DV1020 BurettesGlass titration beaker ME-101446XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Filtration. The precipitate has to beclassified as special waste. The liquidphase has to be disposed as organicwaste.

Wastedisposal

Preparation and Procedures30 mL, kerosineSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

Sensor input: InLab201 glass electrodeRef. input: Sulfidized Ag850 electr.

Indication

Mercaptan Sulfur Content in Kerosine According to ASTM D3227-04a

1) Dissolved oxygen is removed by purging the solvent and thetitrant solutions with nitrogen gas for at least 10 min prior touse. The solutions must be kept protected from atmosphere.

2) Before sample analysis a blank value titration is determined(result is stored as B[ASTM D 3227]).

3) Reagents addition:- 20 mL solvent ASTM D3227-04a are added into the beaker.- 2 mL approx. 360 mg/L ethyl mercaptan standard solution areadded to spike the sample since the content is too low.These steps have been performed using an additional dosingunit. They can be performed manually using a pipette.

4) A Rondolino sample changer with a diaphragm pump wasused. The conditioning time was set to 30 s while the rinsingtime was defined to 2 s (Rondolino settings: 7). The electrode iscleaned with solvent before starting the subsequent sample.

5) For accurate sampling, kerosine was added with a pipetteinstead of weighing (volatility). Thus, its density must be takeninto account. The density of flight petrol was measured using aMETTLER TOLEDO DR45 density meter (d = 0.7905 g/cm3 ,25°C)


2) A fully automated procedure is performed by using twoadditional burette drives and a sample changer. It can be easilymodified for manual operation. Select "Manual stand" in themethod function "Titration stand".

3) ASTM D3227-04a alkaline solvent:Dissolve 1.6 g anhydrous sodium acetate (NaC2H3O2) in 25 mLof deion. water and pour into 1 L flask. Fill up to the mark with2-propanol. This solvent allows a good dissolution of the oil.

4) Sulfidation of the Ag850 electrode:Place the electrode during 10 minutes in an 2% aqueoussodium sulfide solution. Subsequently, place it in a 10%aqueous sodium sulfide solution during 12 h (over night).

5) The 0.02 mol/L mercaptan standard is prepared bydissolving approx. 1.24 g ethyl mercaptan in a 1 L volumetricflask and filling up with the ASTM D3227 solvent.Literature:1) METTLER TOLEDO Appl. brochure 20, ME-51 725 020.2) ASTM D3227-04a, see www.astm.org

Remarks

R1: Mercaptan content (mg/kg)

R1 = (Q-B[ASTM D 3227])*C/(m*d),C = M*1000/z

B[ASTM D3227]: Blank value ofmercaptan standard solution

Calculation

The content of (thiol mercaptan) sulfur in kerosine is determined by precipitation titration in non aqueoussolvent using silver nitrate in 2-propanol. The content is expressed as sulfur, S2-.

Standard NaCl, c(NaCl) = 0.01 mol/L , 5 mL


100


Flight petrol 57354

Addition of 2 mL 0.02 mol/L ethyl mercaptan standard solutionConsumption: approx. 2.8 mL

All results Method-ID M433 Sample Kerosine (1/1) R1 (Content) 15.07 mg/kg Sample Kerosine (1/2) R1 (Content) 14.31 mg/kg Sample Kerosine (1/3) R1 (Content) 14.28 mg/kg Sample Kerosine (1/4) R1 (Content) 14.75 mg/kg Sample Kerosine (1/5) R1 (Content) 13.48 mg/kg

Statistics Method-ID M433 R1 Content Samples 5 Mean 14.34 mg/kg s 0.60 mg/kg srel 4.172 %-----------------------------------------------------------------------

Without addition of ethyl mercaptan standard solutionConsumption: approx. 1 mL

All results Method-ID M433 Sample Kerosine (1/1) R1 (Content) 15.07 mg/kg ............................... Sample Kerosine (1/8) R1 (Content) 14.33 mg/kg Sample Kerosine (1/9) R1 (Content) 12.85 mg/kg

Statistics Method-ID M433 R1 Content Samples 9 Mean 14.04 mg/kg s 1.23 mg/kg srel 8.741 %

Titration curve

Results

101

Method M433 Mercaptan sulfur ASTM D3227 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M433 Title Mercaptan sulfur ASTM D3227

Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Kerosine Entry type Fixed volume Volume 30.0 mL Density 0.7905 g/mL Correction factor 1.0 Temperature 25.0°C


004 Dispense (normal) [1] Titrant ASTM D3227 solvent Concentration 1 Volume 20.0 mL Dosing rate 60.0 mL/min

005 Dispense (normal) [2] Titrant Mercaptan Standard Concentration 0.019 Volume 2.0 mL Dosing rate 60.0 mL/min


007 Titration (EQP) [1]Titrant Titrant AgNO3 in 2-Propanol Concentration 0.01 mol/LSensor Type mV Sensor InLab201 Unit mVTemperature acquisition Temperature acquisition NoStirrer Speed 40%Predispense Mode Volume Volume 0.5 ml Wait time 10 sControl Control User Titrant addition Dynamic dE(set value) 8.0 dV(min) 0.05 mL dV(max) 0.4 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 2 s t(min) 10 s t(max) 30 sEvaluation and Recognition Procedure Standard Threshold 200 mV/mL Tendency Negative Ranges 0 Add. EQP criteria Steepest jump Steepest jump 1


008 Calculation R1 Result Content Result unit mg/kg Formula R1=(Q-B[ASTM D3227])*C/(m*d) Constant C=M*1000/z M M[Mercaptan sulfur] z z[Mercaptan sulfur] Decimal places 2 Result limits No Add. statistics functionalities No

009 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration functions dE/dV - V Last titration functions log dE/dV - V No d2E/dV2 - V No E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No

010 End of sample

102

M434


10 mL deionised water10 mL mixed indicator*60 mL chloroform*see Preparation and Procedures





+ + C12H25O4S - =C27H42NO2-C12H25O4S

1 DV1010 and 1 DV1020 BurettesTwo-phase titr. beaker ME-51107655XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO

Separation of chloroform and finaldisposal as halogenated organicwaste. Neutralization of the aqueousphase.

Wastedisposal


Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DP5 PhototrodeTM , 520 nmIndication

Anionic Surfactant Content in Liquid Detergents by Two-Phase Titration

CAUTION:Chloroform is toxic. Work in a fume hood1) Add 10 mL of deionised water into the titration beaker.2) Add 10 mL of mixed indicator solution.3) Add 60 mL of chloroform. This step was performed wiht anadditional dosing unit. It can be done manually with a pipette.4) Add 5 mL of an liquid detergent solution.

Liquid detergent solution:The concentration was chosen to get an approx. titrantconsumption of 5 mL. Its value is stored as auxiliary valueH[SDS] in g/mL.Preparation: Dissolve ca. 8 g into a 1 L volumetric flask and fillup with deionised water (here: 8.5856 g liquid detergent,0.0429 g/5 mL.).

DP5 PhototrodeTM:After turning on the PhototrodeTM, wait for 15-10 minutes beforestarting analysis to achieve a stable light intensity. Check thetransmission signal of the phototrode in deionised water andset it to 1000 mV by turning the knob on the top of it.

Literature:Application M606, Titration Applications Brochure 22,"Surfactant Titration", ME-51 725 015 .


2) Avoid the formation of air bubbles during the separation timesince they disturb the photometric indication. Thus, select theappropriate stirring speed.

3) Mixed indicator solution:3.1. Dimidium bromide: Weigh accurately 0.2 g into a 100 mLvolumetric flask and dissolve the dye with 10% (v/v) ethanol. Ifnecessary, warm gently to achieve complete dissolution. Aftercooling, fill with 10% (v/v) ethanol to the mark. CAUTION:Dimidium bromide is toxic. Work under appropriate conditionse.g. wear gloves.3.2. Disulfine Blue VN: Weigh accurately 0.1 g into asecond100 mL volumetric flask and dissolve the dye with 10%(v/v) ethanol. If necessary, warm gently. After cooling, fill with10% (v/v) ethanol to the mark.3.3. MIxed indicator solution: 10 dimidium bromide solution,10 mL disulfine blue solution and 10 mL 2.5 mol/L (245 g/L)sulfuric acid solution (be careful: the solution can become hot)are poured into a 250 mL volumetric flask. The solution isdiluted to the mark with deionised water. Store in the dark.

Remarks

R1: SDS-Content (%)

R1 = Q*C/m,C = M/(10*z) ; z = 1

Calculation

The anionic surfactant content in liquid dish washer as SDS (sodium dodecyl sulfate) is determined byprecipitation titration with Hyamine 1622, a cationic surfactant. The content is determined by colorimetrictwo-phase titration with the DP5 Phototrode (automated Epton titration).

Standard SDS, 1 mL 0.01 mol/L aliquot


103




Titration curve

Results

104

Method M434 SDS content (2-phase) 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M434 Title SDS content (2-phase) Author METTLER TOLEDO Date/Time 02.08.2006 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 Liquid detergent solution Entry type Fixed volume Volume 5.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C


004 Dispense (normal) [1] Titrant Chloroform Concentration 1 Volume 60 mL Dosing rate 60.0 mL/min


006 Titration (2-phase) [1]Titrant Titrant Hyamine 1622 Concentration 0.004 mol/LSensor Parameters Type Phototrode Sensor DP5 Unit mVTemperature acquisition Temperature acquisition NoStir Speed 60%Predispense Mode Volume Volume 2.5 mL Wait time 5 sControl Control User Titrant addition Incremental dV 0.15 mL Meas. val. acquisition Fixed time Mix time 5 s Separation time 40 s Stir speed (S. time) 20 %Evaluation and Recognition Procedure Standard Threshold 8 mV/mL Tendency Positive Ranges 1 Lower limit 1 120 mV Upper limit 1 500 mV Add. EQP criteria NoTermination At Vmax 6.0 mL At potential No At slope No After number of recognized EQPs No Combined termination criteria No


008 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V Last titration function log dE/dV - V No d2E/dV2 - V No E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No Condition No

End of sample

105

M435

Potassium hydrogen phthalate, KHPM = 204.23; z = 1



Titration Excellence T50/T70/T901 DV1010 BuretteXS205 Balance

NaOH + HOOC-C6H4-COOK =Na+ + K+ + -OOC-C6H4-COO-

Glass titration beaker ME-101446Drying tube ME-23961Drying tube holder ME-23915Olivetti Printer JobJet 210

METTLER TOLEDO


Wastedisposal

Preparation and ProceduresPrimary standardPotassium hydrogen phthalate70 - 120 mg

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG111-SCIndication

Titer Determination of NaOH 0.1 mol/L

1) The DG111-SC electrode is calibrated before analysis usingMETTLER TOLEDO buffers pH 4.01, 7.00 and 9.21.

2) Approximately 0.1 g potassium hydrogen phthalate areadded to the titration beaker.

3) 50 mL deionized water are added to the beaker.

4) The titration method is started.

1) Glass beakers are recommended in order to avoid anyinterference during weighing due to electrostatic effects.

2) To keep the titer of the sodium hydroxide constant, it isimportant to avoid intake CO2 from the air which leads to theformation of carbonate. This is achieved by using a suitableadsorbing medium i.e. sodium hydroxide on support. It is filledin a drying tube (cup ME-23961, holder ME-23915) on top ofthe burette holder.

3) The mean value of the titer is automatically stored as part ofthe setup data by the function TITER.

Remarks

Titer :

R1=m/(VEQ*c*C)C=M/(10*p*z)

Calculation

Method for the standardization of 0.1 mol/L sodium hydroxide. The method can be used with minor changesfor the titer determination of most aqueous strong base titrants.

Standard --

Thomas HitzAuthor

106


All results Method-ID M435 Sample Potassium hydrogen phthalate (1/1) R1 (Titer) 0.99714 Sample Potassium hydrogen phthalate (1/2) R1 (Titer) 0.99372 Sample Potassium hydrogen phthalate (1/3) R1 (Titer) 0.99240 Sample Potassium hydrogen phthalate (1/4) R1 (Titer) 0.99240

Statistics Method-ID M435 R1 Potassium hydrogen phthalate Samples 4 Mean 0.99392 s 0.00224 srel 0.225 %

Titration curve

Results

107

Method M435 Titer 0.1 mol/L NaOH 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M435 Title Titer 0.1 mol/L NaOH Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample (Titer) Titrant NaOH Concentration 0.1 mol/L Standard Potassium hydrogen phthalate Type of standard Solid Entry type Weight Lower limit 0.08 g Lower limit 0.12 g Correction factor 1.0 Temperature 25.0°C Entry Arbitrary



005 Titration (EQP) [1]Titrant Titrant NaOH Concentration 0.1 mol/LSensor Type pH Sensor DG111-SC Unit pHTemperature acquisition Temperature acquisition NoStir Speed 35%Predispense Mode None Wait time 0 sControl Control User Titrant addition Dynamic dE(set value) 12.0 mV dV(min) 0.002 mL dV(max) 0.5 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 1 s t(min) 5 s t(max) 30 sEvaluation and Recognition Procedure Standard Threshold 5 pH/mL Tendency Positive Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method006 Calculation R1 Result Titer Result unit -- Formula R1=m/(VEQ*c*C) Constant C=M/(10*p*z) M M[Potassium hydrogen phthalate] z z[Potassium hydrogen phthalate] Decimal places 5 Result limits No Add. statistics functionalities No


008 End of sample

009 Titer Titrant NaOH Concentration 0.1 mol/L Titer= Mean[R1] Result limits No

010 Calculation R2 Result Mean Titer Result unit -- Formula R2=Mean[R1] Constant C=1 M M[Potassium hydrogen phthalate] z z[Potassium hydrogen phthalate] Decimal places 5 Result limits No Add. statistics functionalities Yes


108

M436

--

--

--


--

Titration beaker ME-101974

METTLER TOLEDO

Neutralization before final disposalWastedisposal

Preparation and Procedures60 mL METTLER TOLEDO BufferspH 4.01 / pH 7.00 / pH 9.21

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG111-SCIndication

Calibration of a pH Electrode

1) Three titration beakers are filled with 60 mL of each pHbuffers solutions i.e. pH 4.01, 7.00 and 9.21 .The pH buffer solutions are defined as a pH buffer list "METTLERTOLEDO (Ref. 25°C) pH".

2) Connect the first beaker to the titration stand and start themethod.

3) After measurement of each pH buffer solution the electrode iscleaned with deionized water before starting the next sample.

1) The calibration data are automatically stored in the setupdata of the titrator. They are assigned to the sensor used in themethod and are only valid for this sensor.

2) The reference data (temperature table) of the METTLERTOLEDO buffers are stored into the titrator. These buffers can beselected from the menu and stored in a buffer list, if frequent useis requested.

3) If the sensor is used at a different temperature at a later time,the titrator corrects the slope of the sensor according to theNernst equation by manual entry or temperature measurementwith a T-sensor.

4) More details can be found in "Fundamentals ofTitration"(ME-704153) and in the T50/T70/t90 operatinginstructions.

Remarks

R1=E ; mV

Potential measurement of the buffersolutions

Calculation

A general purpose pH sensor adjustment (calibration) method.

Standard --


109


All results

Method M436

R1 (Potential) 174.5 mV (1/1) pH 4.01 R1 (Potential) 0.0 mV (1/2) pH 7.00 R1 (Potential) -129.5 mV (1/3) pH 9.21

Calibration Sensor DG111-SC Buffer list METTLER TOLEDO (Ref. 25°C) pH

Calibration temperature 25.0°C Number of segments 1

Slope (TCalib) -58.80 mV/pH Zero point 7.027 pH

Titration curve

Results

110

Method M436 Calibration DG111-SC 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M436 Title Calibration DG111-SC Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample (Calib) Sensor type pH Sensor DG111-SC Unit pH Automatic buffer recognition No pH buffer list METTLER TOLEDO (Ref. 25°C)pH Calibration Linear Buffer 1 4.01 Buffer 2 7.00 Buffer 3 9.21 Temperature 25.0°C

003 Titration stand (Manual Stand) Type Manual stand Titration stand Manual Stand 1


005 Measure (normal)[1]Sensor Type pH Sensor DG111-SC Unit mVTemperature acquisition Temperature acquisition NoStir Speed 30 %Acquisition of measured values Acquisition Equilibrium controlled dE 0.5 mV dt 1 s t(min) 3 s t(max) 30 s Mean value No

006 Calculation R1 Result Potential Result unit mV Formula R1=E Constant C=1 M M[None] z z[None] Decimal places 2 Result limits No Add. statistics functionalities No

007 End of sample

008 Calibration Sensor DG111-SC Limits No

009 Record Results Yes Raw results Yes Resource data No Calibration curve Yes Method No Series data No Condition No

Method

111

M437

Hydrochloric acid, HClM=36.46 g/mol, z=1



Titration Excellence T50/T70/T901 Conductivity Board ME-51109840


DV1010 BuretteTitration beakers ME-101974XS205 BalanceOlivetti Printer JobJet 210

METTLER TOLEDO


Wastedisposal

Preparation and Procedures0.4% hydrochloric acid,approx. 3-10 g

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

InLab717Indication

Hydrochloric Acid Content by Conductometric Titration

1) Install the InLab717 conductometric sensor by connecting itto the conductivity board (CB).

2) Perform a titer determination using potassium hydrogenphthalate (KHP) as a primary standard: 70-120 mg KHP aredissolved into 50 mL deionized water in a titration beaker.

3) Sample titration:Add 3-10 g hydrochloric acid solution into the titration beakerand dilute it with 50 mL deionized water.

4) The sample is titrated with 0.1 mol/L NaOH solution.

5) The sensor is rinsed with deionized water after each titration.


Remarks

Content (%) :

R1 = Q*C/mC=M/(z*10)

Calculation

The hydrochloric acid content is determined by neutralization titration with sodium hydroxide as a titrant. Theconductivity of the titration is monitored by an InLab717 conductometric sensor.

Standard Potassium hydrogen phthalate, KHP, 70-120 mg


112


All results Method-ID M437 Sample HCl solution (1/1) R1 (Content) 0.364 % Sample HCl solution (1/2) R1 (Content) 0.362 % Sample HCl solution (1/3) R1 (Content) 0.364 % Sample HCl solution (1/4) R1 (Content) 0.364 % Sample HCl solution (1/5) R1 (Content) 0.362 % Sample HCl solution (1/6) R1 (Content) 0.363 %


Titration curve

Results

113

Method M437 HCl content conductometric 02.08.2006Author METTLER TOLEDO

001 Title Type General titration Compatible with T50 / T70 / T90 ID M437 Title HCl content conductometric Author METTLER TOLEDO Date/Time 02.08.2006 15:00:00 Modified -- Modified by -- Protect No SOP None

002 Sample Number of IDs 1 ID 1 HCl solution Entry type Weight Lower limit 3.0 g Upper limit 10.0 g Density 1 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary

003 Titration stand (Manual stand)Type Manual standTitration stand Manual stand 1


005 Titration (EQP) [1]Titrant Titrant NaOH Concentration 0.1 mol/LSensor Type Conductivity Sensor InLab717 Unit μSTemperature acquisition Temperature acquisition NoStir Speed 30%Predispense Mode Volume Volume 3 mL Wait time 10 sControl Control User Titrant addition Incremental dV 0.1 mL Meas. val. acquisition Equilibrium controlled dE 1.0 μS dt 2 s t(min) 3 s t(max) 30 sEvaluation and Recognition Procedure Segmented Threshold 500 μS/mL2

Ranges 0 Add. EQP criteria NoTermination At Vmax 10.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No

Method006 Calculation R1 Result Content Result unit % Formula R1=Q*C/m Constant C=M/(10*z) M M[Hydrochloric acid] z z[Hydrochloric acid] Decimal places 3 Result limits No Add. statistics functionalities No

007 Record Results Per series Raw results Per series Table of measured values Last titration function Sample data Per series Resource data No E - V Last titration function dE/dV - V No log dE/dV - V No d2E/dV2 - V Last titration function E - t No V - t No dV/dt - t No T - t No E - V & dE/dV - V No V - t & dV/dt - t No Calibration curve No Method No Series data No Condition No

008 End of sample

114

METTLER TOLEDO

115

METHOD TEMPLATES Method template “EQP”

Method template “EP”

Method template “Stating”

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (EQP) [1] 6 Calculation R1 7 Calculation R2 8 Calculation R3 9 Record 10 End of sample

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (EP) [1] 6 Calculation R1 7 Calculation R2 8 Calculation R3 9 Record 10 End of sample

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Stating [1] 6 Calculation R1 7 Calculation R2 8 Calculation R3 9 Calculation R4 10 Calculation R5 11 Record 12 End of sample

METTLER TOLEDO

116

Method template “Measure”

Method template “2-phase”

Method template “Learn-EQP”

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Measure (normal) [1] 6 Calculation R1 11 Record 12 End of sample

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (2-phase) [1] 6 Calculation R1 7 Calculation R2 8 Calculation R3 11 Record 12 End of sample

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (Learn-EQP) [1] 6 Calculation R1 7 Calculation R2 8 Calculation R3 11 Record 12 End of sample

METTLER TOLEDO

117

Method template “Titer with EQP”

Method template “Titer with EP”

Method template “Calibration”

Nr. Method Function 1 Title 2 Sample (Titer) 3 Titration stand (Manual stand) 4 Stir 5 Titration (EQP) [1] 6 Calculation R1 7 Record 8 End of sample 9 Titer 10 Calculation R2 11 Record

Nr. Method Function 1 Title 2 Sample (Titer) 3 Titration stand (Manual stand) 4 Stir 5 Titration (EP) [1] 6 Calculation R1 7 Record 8 End of sample 9 Titer 10 Calculation R2 11 Record

Nr. Method Function 1 Title 2 Sample (Calib) 3 Titration stand (Manual stand) 4 Stir 5 Measure (normal) [1] 6 Record 7 End of sample 8 Calibration 9 Record

METTLER TOLEDO

118

Method template “Calibration segmented”

Method template “Blank with EQP”

Method template “Blank with EP”

Nr. Method Function 1 Title 2 Sample (Calib) 3 Titration stand (Manual stand) 4 Stir 5 Measure (normal) [1] 6 Record 7 End of sample 8 Calibration 9 Record

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (EQP) [1] 6 Calculation R1 7 Record 8 End of sample 9 Blank 10 Calculation R2 11 Record

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (EP) [1] 6 Calculation R1 7 Record 8 End of sample 9 Blank 10 Calculation R2 11 Record

METTLER TOLEDO

119

Method template “EP / EQP”

Method template “EQP / EQP”

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (EP) [1] 6 Calculation R1 7 Stir 8 Titration (EQP) [2] 9 Calculation R2 10 Calculation R3 11 Calculation R4 12 Record 13 End of sample

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (EQP) [1] 6 Calculation R1 7 Calculation R2 8 Calculation R3 9 Stir 10 Titration (EQP) [2] 11 Calculation R4 12 Calculation R5 13 Calculation R6 14 Record 15 End of sample

METTLER TOLEDO

120

Method template “EP / EP”

Method template “Titer with EQP & EQP”

Nr. Method Function 1 Title 2 Sample 3 Titration stand (Manual stand) 4 Stir 5 Titration (EP) [1] 6 Calculation R1 7 Calculation R2 8 Calculation R3 9 Stir 10 Titration (EP) [2] 11 Calculation R4 12 Calculation R5 13 Calculation R6 14 Record 15 End of sample

Nr. Method Function 1 Title 2 Sample (Titer) 3 Titration stand (Manual stand) 4 Stir 5 Titration (EQP) [1] 6 Calculation R1 7 Record 8 End of sample 9 Titer 10 Calculation R2 11 Record 12 Sample 13 Titration stand (Manual stand) 14 Stir 15 Titration (EQP) [2] 16 Calculation R3 17 Calculation R4 18 Calculation R5 19 Record 20 End of sample

METTLER TOLEDO

121

Method template “Titer with EP & EP”

Method template “Calibration & EQP”

Nr. Method Function 1 Title 2 Sample (Titer) 3 Titration stand (Manual stand) 4 Stir 5 Titration (EP) [1] 6 Calculation R1 7 Record 8 End of sample 9 Titer 10 Calculation R2 11 Record 12 Sample 13 Titration stand (Manual stand) 14 Stir 15 Titration (EP) [2] 16 Calculation R3 17 Calculation R4 18 Calculation R5 19 Record 20 End of sample

Nr. Method Function 1 Title 2 Sample (Calib) 3 Titration stand (Manual stand) 4 Stir 5 Measure (normal) [1] 6 Record 7 End of sample 8 Calibration 9 Record 10 Sample 11 Titration stand (Manual stand) 12 Stir 13 Titration (EQP) [1] 14 Calculation R1 15 Calculation R2 16 Calculation R3 17 Record 18 End of sample

METTLER TOLEDO

122

Method template “Calibration & EP”

Nr. Method Function 1 Title 2 Sample (Calib) 3 Titration stand (Manual stand) 4 Stir 5 Measure (normal) [1] 6 Record 7 End of sample 8 Calibration 9 Record 10 Sample 11 Titration stand (Manual stand) 12 Stir 13 Titration (EP) [1] 14 Calculation R1 15 Calculation R2 16 Calculation R3 17 Record 18 End of sample

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Method template “Calibration & Titer with EQP & EQP”

Nr. Method Function 1 Title 2 Sample (Calib) 3 Titration stand (Manual stand) 4 Stir 5 Measure (normal) [1] 6 Record 7 End of sample 8 Calibration 9 Record 10 Sample (Titer) 11 Titration stand (Manual stand) 12 Stir 13 Titration (EQP) [1] 14 Calculation R1 15 Record 16 End of sample 17 Titer 18 Calculation R2 19 Record 20 Sample 21 Titration stand (Manual stand) 22 Stir 23 Titration (EQP) [2] 24 Calculation R3 25 Calculation R4 26 Calculation R5 27 Record 28 End of sample

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Method template “Calibration & Titer with EP & EP”

Nr. Method Function 1 Title 2 Sample (Calib) 3 Titration stand (Manual stand) 4 Stir 5 Measure (normal) [1] 6 Record 7 End of sample 8 Calibration 9 Record 10 Sample (Titer) 11 Titration stand (Manual stand) 12 Stir 13 Titration (EP) [1] 14 Calculation R1 15 Record 16 End of sample 17 Titer 18 Calculation R2 19 Record 20 Sample 21 Titration stand (Manual stand) 22 Stir 23 Titration (EP) [2] 24 Calculation R3 25 Calculation R4 26 Calculation R5 27 Record 28 End of sample

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APPLICATION MODES Sensor type pH Units pH and mV Application mode “Acid / base” Control Cautious Normal Fast Mode Acid / baseShow parameters YesTitrant addition DynamicdE(set value) [mV] 10.0 12.0 18.0 dV(min) [mL] 0.002 0.002 0.002 dV(max) [mL] 0.2 0.5 0.75 Meas. val. acquisition Equilibrium controlleddE [mV] 0.5 0.5 1.0 dt [s] 2 1 1 t(min) [s] 3 3 2 t(max) [s] 30 30 20 Application mode “Acid / base (non aq.)” Control Cautious Normal Fast Mode Acid / base (non aq.)Show parameters YesTitrant addition DynamicdE(set value) [mV] 10.0 12.0 12.0 dV(min) [mL] 0.05 0.01 0.05 dV(max) [mL] 0.5 0.3 0.5 Meas. val. acquisition Equilibrium controlleddE [mV] 1.0 1.0 1.0 dt [s] 3 2 1 t(min) [s] 5 2 2 t(max) [s] 30 15 10

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Sensor type mV Unit mV Application mode “Precipitation” Control Cautious Normal Fast Mode Precipitation Show parameters Yes Titrant addition Dynamic dE(set value) [mV] 5.0 9.0 12.0 dV(min) [mL] 0.004 0.008 0.01 dV(max) [mL] 0.2 0.4 0.5 Meas. val. acquisition Equilibrium controlled dE [mV] 0.5 0.5 1.0 dt [s] 2 1 1 t(min) [s] 3 3 3 t(max) [s] 30 30 20 Application mode “Precipitation (non aq.)” Control Cautious Normal Fast Mode Precipitation (non aq.) Show parameters Yes Titrant addition Incremental dV [mL] 0.075 0.1 0.15 Meas. val. acquisition Equilibrium controlled dE [mV] 1.0 1.0 1.0 dt [s] 5 3 1 t(min) [s] 5 5 3 t(max) [s] 20 15 10 Application mode “Redox” Control Cautious Normal Fast Mode Redox Show parameters Yes Titrant addition Dynamic dE(set value) [mV] 6.0 8.0 18.0 dV(min) [mL] 0.005 0.02 0.03 dV(max) [mL] 0.1 0.2 0.3 Meas. val. acquisition Equilibrium controlled dE [mV] 0.5 1 5.0 dt [s] 2 2 1 t(min) [s] 5 3 1 t(max) [s] 15 10 10

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Sensor type ISE Units mV, ppm, pX, pM Application mode “Precipitation” Control Cautious Normal Fast Mode Precipitation Show parameters Yes Titrant addition Dynamic dE(set value) [mV] 8.0 8.0 8.0 dV(min) [mL] 0.005 0.02 0.05 dV(max) [mL] 0.15 0.2 0.5 Meas. val. acquisition Equilibrium controlled dE [mV] 0.5 1.0 1.0 dt [s] 2 2 1 t(min) [s] 8 5 4 t(max) [s] 45 30 15 Sensor type Phototrode Units mV, %T, A Application mode “Precipitation” Control Cautious Normal Fast Mode Precipitation Show parameters Yes Titrant addition Incremental dV [mL] 0.05 0.1 0.15 Meas. val. acquisition Equilibrium controlled dE [mV] 0.5 1.0 3.0 dt [s] 1 1 1 t(min) [s] 6 5 3 t(max) [s] 30 15 6 Application mode “Complexation” Control Cautious Normal Fast Mode Complexation Show parameters Yes Titrant addition Incremental dV [mL] 0.01 0.01 0.04 Meas. val. acquisition Equilibrium controlled dE [mV] 0.5 2.0 8.0 dt [s] 2 1 1 t(min) [s] 5 3 1 t(max) [s] 40 20 15

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Sensor type Polarized Unit mV Application mode “Redox” Control Cautious Normal Fast Mode Redox Show parameters Yes Titrant addition Incremental dV [mL] 0.04 0.05 0.08 Meas. val. acquisition Equilibrium controlled dE [mV] 1.0 2.0 2.0 dt [s] 1 1 1 t(min) [s] 3 2 2 t(max) [s] 30 30 20 Sensor type Polarized Unit µA Application mode “Redox” Control Cautious Normal Fast Mode Redox Show parameters Yes Titrant addition Incremental dV [mL] 0.1 0.1 0.2 Meas. val. acquisition Equilibrium controlled dE [uA] 0.1 0.3 0.5 dt [s] 2 2 1 t(min) [s] 10 5 3 t(max) [s] 30 30 15

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Sensor type Temperature Units oC, K, oF Application mode “Acid / base” Control Cautious Normal Fast Mode Acid / base Show parameters Yes Titrant addition Incremental dV [mL] 0.1 0.15 0.2 Meas. val. acquisition Equilibrium controlled dT [oC] / [K] / [oF] 0.5 / 0.5 / 1.0 1.0 / 1.0 / 2.0 2.0 / 2.0 / 4.0dt [s] 1 1 1 t(min) [s] 6 3 2 t(max) [s] 30 20 10 Sensor type Conductivity Units mS, mS/cm, µS, µS/cm Application mode “Acid / base” Control Cautious Normal Fast Mode Acid / base Show parameters Yes Titrant addition Incremental dV [mL] 0.05 0.1 0.2 Meas. val. acquisition Equilibrium controlled

1.0 1.0 3.0 dE [µS] bzw. [µS/cm] dE [mS] bzw. [mS/cm] 0.01 0.01 0.01 dt [s] 1 1 1 t(min) [s] 3 3 2 t(max) [s] 30 30 20 Application mode “Precipitation” Control Cautious Normal Fast Mode Precipitation Show parameters Yes Titrant addition Incremental dV [mL] 0.05 0.1 0.2 Meas. val. acquisition Equilibrium controlled

0.2 1.0 3.0 dE [µS] bzw. [µS/cm] dE [mS] bzw. [mS/cm] 0.01 0.01 0.01 dt [s] 1 1 1 t(min) [s] 3 3 2 t(max) [s] 30 30 10

The methods in this brochure represent selected, possible application examples. These have been tested with all possible care with the analytical instruments mentioned in the brochure. The experiments were conducted and the resulting data evaluated based on our current state of knowledge. However, the applications do not absolve you from personally testing their suitability for your intended methods, instruments and purposes. As the use and transfer of an application example are beyond our control, we cannot accept responsibility therefore. When chemicals and solvents are used, the general safety rules and the directions of the manufacturer must be observed.

For more informationwww.mt.com

This application brochure is the first to cover the Titration Excellence instruments T50, T70 and T90. It describes the unique possibilities these titrators offer in order to find the optimal method for your purposes.

How easily methods can be created and edited is briefly described in the introduction chapter. The concept of ready-to-use METTLER TOLEDO meth-ods is explained in the following. Further features that support efficient method development such as method templates and application modes are described in addition.

All METTLER TOLEDO methods (including procedures, literature references and results) which are available in every model are shown in detail. Fur-thermore, the structure of all pre-programmed method templates is listed and the parameters of all available application modes are specified.

Enjoy an easy and efficient method development in all models of the Titration Excellence line.

For more information

Application Brochure 34Selected METTLER TOLEDO Methods for Titration Excellence Line

T50A Terminal T70 with Terminal and two additional dosing units

Mettler-Toledo AG, AnalyticalSonnenbergstrasse 74CH-8606 Schwerzenbach, SwitzerlandTel. +41-44 806 77 11Fax +41-44 806 73 50

Subject to technical changes.©11/2006 Mettler-Toledo AGPrinted in Switzerland, ME-51725066AMarkt Support AnaChem

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Titration Excellence AGC Book 20% Cyan - ::: BK ...bikeitech.com/DATAS/es_free3/f_49780bd55e351.pdfAGC Book 20% Cyan 34 Application brochure Titrators T50 T70 T90 Selected METTLER