metler toledo ttitrator

METTLER TOLEDO Titrators

Characteristic ValuesApplications brochure 10

Dedicated to Mr. Kees Mooibroek

METTLER TOLEDO Titrators Characteristic Values

Characteristic Values METTLER TOLEDO Titrators


Contents

M084 Determination of Acid Values in Organic Solvents, Oils, Fats, Polymers ...................... 1

M228 Acid Number of Castor Oil .................................................................................... 4

M229 Acid NUmber of Cosmetic Creams......................................................................... 7

M230 Neutralizing Value of Baking Powder................................................................... 10

M231 Acid Number of Polyester ................................................................................... 13

M076 Free Fatty Acid of Oil and Fat .............................................................................. 16

M086 Epoxide Values ................................................................................................. 19

M232 Epoxide Value of 2,3-Epoxypropylene-Phenyl Ether .............................................. 22

M087 Bromine Number of Petroleum Distillates and Aliphatic Olefins ............................... 25

M233 Low Bromine Index Determination of a Standard Solution ...................................... 28

M090 Determination of Saponification Value ................................................................. 31

M091 Determination of Hydroxyl Value ......................................................................... 34

M234 Hydroxyl Value of Polyols .................................................................................. 37

M095 Determination of Isocyanate Content ................................................................... 40

M235 NCO-Content of Isocyanates by Back-Titration ...................................................... 43

M236 Determination of Free HCl and Isocyanates .......................................................... 46

M096 Iodine Value in Resins and Oils According to Wijs ................................................. 49

M051 Iodine Value of Edible OIls and Fats According to Wijs (AOAC Method 28.023) ........ 52

M211 Iodine Value of Cosmetic Fats According to Wijs ................................................... 55

M206 Determination of Carboxyl Groups in PET ............................................................ 58

M237 Peroxide Value of Lecithin .................................................................................. 61

M624 Peroxide Value of Edible Oils and Fats ................................................................. 64

M238 Determination of Permanganate Index in Waste Water .......................................... 67

M239 Chemical Oxygen Demand (COD) of Waste Water ................................................ 70

M517 Blank Determination According to ASTM D664-89................................................ 73

M518 Blank Determination According to ASTM D4739-92.............................................. 76

M519 Acid Number (AN) According to ASTM D664-89 .................................................. 79


M520 Base Number (BN) According to ASTM D4739-92 ............................................... 82

M057 TBN According to ASTM D2896-85 .................................................................... 85

M058 TBN According to ASTM D4739-87 .................................................................... 88

M059 TAN According to ASTM D664-89 ....................................................................... 91

M099 Conductometric Base Number Titration of Motor Oil............................................... 94

M100 Standardization of HCl in Isopropanol by Conductometric Titration .......................... 97

M061 pH, Acidity, Lactone and Formol Value of Honey................................................. 100

M240 Formol Number, Acidity and True Brix Value of Orange Juice ............................... 103

M241/1 Carbon Black Surface Area (ASTM D3765-99): Standardization .......................... 106

M241/2 Carbon Black Surface Area (ASTM D3765-99): Linear Regression........................ 109

M241/3 Carbon Black Surface Area (ASTM D3765-99): Sample Titration .......................... 112

M242 Determination of Amine Number ....................................................................... 115

M243 Free Available Chlorine Residual in Water According to ASTM D1253-86 .............. 118

M244 Total Residual Chlorine in Water According to ASTM D1253-86 ........................... 121

M258 Total Base Number According to DIN ISO 3771 .................................................. 124

M259 CTAB Surface Area on Amorphous Silica ............................................................ 127

M084

Acidic components

40 mL solvent mixture:Toluene:ethanol 2:1

KOH in Ethanol:c(KOH) = 0.1 mol/L,c(KOH) = 0.01 mol/L

DL50Graphix, DL53/55/58DL70ES, DL77

OH- + H+ = H2O

1 additional burette DV1005,1 additional burette DV1020100 mL titration beaker ME-101974AT261 balance, Printer

METTLER TOLEDO

Organic solvent waste (chlorinated andnot chlorinated)

Wastedisposal

Preparation and ProceduresOrganic solvents, resins, oils, fats fattyacids, softeners, polymers

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Determination of Acid Values in Organic Solvents, Oils, Fats, Polymers

Solvent mixture according to DIN 53402 (1973):Toluene:ethanol 2:1

Hints:1) Ensure good stirring. Speed and stirring time can be adaptediaccording to the viscosity or the bad solubility of the sample.

2) If the dissolution of the sample is not straightforward, heatingmy be applied to improve it. Ultrasonics can also be applied.

3) The titration can also indicated photometrically by aphototrode and a color indicator. It can be affected by thelimitations of the indicators, by the formation of precipitates, orby change in turbidity.

4) Use the same amount of solvent mixture for the blank as wellas for the sample determination.

5) Substances which undergo side reactions with the alkalinetitrant can not be titrated.

This application describes the determination of the acid value ofresins, oils, fats, fatty acids, solvents, softeners, polymers andother technical organic products.

Due to better solubility properties, this kind of titration is oftencarried out in a binary solvent mixture. The titrant is dissolved ina solvent wich is miscible with the solvent mixture, i.e. inethanol or methanol. If needed, an auxiliary solvent like acetonecan be added to improve solubility.

The whole acidic components are neutralized, including half ofthe acid anhydride. Since the content of free anhydride is small,this error can be generally neglected. On the other hand, ifsignificant amounts of anhydride are present, an additionaltitration with aqueous potassium hydroxide solution must beperformed to determine the second missing half anhydride.

Literature:DIN 53402, 51588ISO 3682

Remarks

Blank determination (Meth. 084B):R1 = QR1 is stored as aux. value H8

Acid value determination (Meth: 084A):R1 = (Q1 - H8)*C1/m ; C1 = 56.1

Calculation

The acid number is the amount of potassium hydroxide used to neutralized acidic components in differentsamples (mg KOH/g). Here the determination of the acid value according to DIN 53402 (1973) ispresented.

Standard Potassium hydrogen phthalate

Kees MooibroekAuthor

1

Table of measured values

Method 084A Acid Values, Solvent Blank 13-Apr-1994 10:38User K.M.Measured 13-Apr-1994 11:09RESULTS No ID1 ID2 Sample amount and results 1/1 Solv.Bl. Blank 40.0 g Weight m R1 = 0.006 mmol Blank Acid No 1/2 Solv.Bl. Blank 40.0 g Weight m R1 = 0.005 mmol Blank Acid No 1/3 Solv.Bl. Blank 40.0 g Weight m R1 = 0.005 mmol Blank Acid No 1/4 Solv.Bl. Blank 40.0 g Weight m R1 = 0.001 mmol Blank Acid No

STATISTICS Number results R1 n = 4 Mean value x = 0.004 mmol Blank Acid No Standard deviation s = 0.002337 mmol Blank Acid No Rel. standard deviation srel = 59.191 % Outlier test : sample No. 1/4 Number results R1 n = 3 Mean value x = 0.004 mmol Blank Acid No Standard deviation s = 0.000592 mmol Blank Acid No Rel. standard deviation srel = 11.626 %

AUXILIARY VALUE New value H8 = 0.005091 Blank Acid No

Method 084B Acid Values (non aqueous) 15-Apr-1994 14:35User K.M.Measured 15-Apr-1994 16:18

RESULTS No ID1 ID2 Sample amount and results 1/1 Acid val Terpentine 43.003 g Weight m R1 = 0.290 mg KOH/g Acid value 1/2 Acid val Terpentine 42.662 g Weight m R1 = 0.304 mg KOH/g Acid value ................................................................ 1/7 Acid val Terpentine 42.896 g Weight m R1 = 0.300 mg KOH/g Acid valueSTATISTICS Number results R1 n = 7 Mean value x = 0.298 mg KOH/g Acid value Standard deviation s = 0.004793 mg KOH/g Acid value Rel. standard deviation srel = 1.606 % Outlier test: no outliers!

Titration curve

Results

2

Method 084B Acid values (non aqueous) Version 15-Apr-1994 14:35

Title Method ID . . . . . . . . . . . . . 084B Title . . . . . . . . . . . . . . . Acid values (non aqueous) Date/time . . . . . . . . . . . . . 15-Apr-1994 14:35Sample Number samples . . . . . . . . . . . 7 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . Acid val Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60Titration Titrant . . . . . . . . . . . . . . KOH (Isoprop.) Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 500 EQP range . . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . +500 Limit B [mV, pH,...] . . . . . -500 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure. . . . . . . StandardCalculation Result name . . . . . . . . . . . . Acid Value Formula . . . . . . . . . . . . . . R1=(Q1-H8)*C1/m Constant . . . . . . . . . . . . . . C1=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod 084A Acid Values, Solvent Blank Version 13-Apr-1994 10:38

Title Method ID . . . . . . . . . . . . . 084A Title . . . . . . . . . . . . . . . Acid Values, Solvent Blank Date/time . . . . . . . . . . . . . 13-Apr-1994 10:38Sample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . SolvBl. Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60Titration Titrant . . . . . . . . . . . . . . KOH (Isoprop.) Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 500 EQP range . . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . +500 Limit B [mV, pH,...] . . . . . -500 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure. . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank Acid No Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Blank Acid No. Formula . . . . . . . . . . . . . . H8=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

3

M228

Acidic components

50 mL toluene1 mL hydrochloric acid

KOH in Ethanol:c(KOH) = 0.1 mol/L,


100 mL titration beaker ME-101974PrinterBalance

METTLER TOLEDO

Organic solvent wasteWastedisposal

Preparation and ProceduresCastor oil, 9-11 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Acid Number of Castor Oil

1 mL hydrochloric acid 0.1 mol/L is added to both solvent andsample solutions (Spiking)

1) One mL hydrochloric acid has been added to both 50 mLsolvent and samle solution to test the system (spiking).

2) The first equivalent point is due to the neutralization of 1 mLhydrochloric acid. The method has been programmed to detectonly the second equivalent point.

Literature:DAB

Remarks

Blank determination (Meth. SZ-bw):R1 = QR1 is stored as auxiliary value H4

Acid value det. (Meth: SZtit):R1 = (Q1 - H4)*C1/mC1 = 56.1

Calculation

Determination of the acid number of castor oil according to DAB (Deutsches Arzneimittelbuch).


Dieter RehwaldAuthor

4


METTLER TOLEDO DL58 Titrator V2.1 Team Ost:ms/rd 030-35503603 RatzFatz *1999* Help-Hotline: 0172-2727849

Method SZtit Säurezahl Rizinulöl/DAB 22-Feb-1999 19:42 Measured 22-Feb-1999 20:48 User DR

ALL RESULTS

No ID Sample amount and results

1 12.4 g R1 = 5.308 ml VBR. TM R2 = 0.601 mg KOH/g Säurezahl 2 9.4 g R1 = 4.989 ml VBR. TM R2 = 0.603 mg KOH/g Säurezahl 3 10.6 g R1 = 5.131 ml VBR. TM R2 = 0.610 mg KOH/g Säurezahl 4 11.6 g R1 = 5.225 ml VBR. TM R2 = 0.602 mg KOH/g Säurezahl 5 9.6 g R1 = 5.034 ml VBR. TM R2 = 0.616 mg KOH/g Säurezahl

STATISTICS Number results R2 n = 4 Mean value x = 0.604 mg KOH/g Säurezahl Standard deviation s = 0.00377 mg KOH/g Säurezahl Rel. standard deviation srel = 0.625 % Sample No. 5 deleted

Titration curve

Results

5

Method SZtit Säurezahl Rizinusöl/DAB Version 22-Feb-1999 19:42

Title Method ID . . . . . . . . . . . . . SZtit Title . . . . . . . . . . . . . . . Säurezahl Rizinusöl/DAB Date/time . . . . . . . . . . . . . 22-Feb-1999 19:42Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 9.0 Upper limit [g] . . . . . . . . . 11.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 20EQP Titration Titrant . . . . . . . . . . . . . . KOH/EtOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.3 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 100 Steepest jump only . . . . . . . Yes Range . . . . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . -100 Limit B [mV, pH,...] . . . . . -500 Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 10.0 at potential . . . . . . . . . . Yes Potential [mV, pH,...] . . . . -450 at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . ml Result name . . . . . . . . . . . . VBR. TM Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R2=(Q-H4)*C2/m Constant . . . . . . . . . . . . . . C2=M/z Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mg KOH/g Result name . . . . . . . . . . . . Säurezahl Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Report Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

MethodMethod SZ-bw Blank value with EQP tit. Version 23-Feb-1999 17:09

Title Method ID . . . . . . . . . . . . . SZ-bw Title . . . . . . . . . . . . . . . Blank value with EQP tit. Date/time . . . . . . . . . . . . . 23-Feb-1999 17:09Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Volume Volume [mL] . . . . . . . . . . . 50.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 20EQP Titration Titrant . . . . . . . . . . . . . . KOH/EtOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.3 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 200 Steepest jump only . . . . . . . Yes Range . . . . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . -100 Limit B [mV, pH,...] . . . . . -500 Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 10.0 at potential . . . . . . . . . . Yes Potential [mV, pH,...] . . . . -450 at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Auxiliary value ID text . . . . . . . . . . . . . . Blindwert Formula . . . . . . . . . . . . . . H4=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

6

M229

Acidic components

25 mL ethanol25 mL toluene

KOH in Ethanol:c(KOH) = 0.1 mol/L



METTLER TOLEDO


Preparation and ProceduresCosmetic creams, 1-2 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Acid Number of Cosmetic Creams

1) A ethanol:toluene 1.1 mixture is used to dissolve thecosmetic creams.

2) To ensure complete dissolution, the sample solution isdissolved under stirring at 40°C.

1) The customer always titrates manually to the phenolphtaleincolour change. Therefore an endpoint titration was performed toan absolute Ep value of -310 mV, although this point has noreal meaning.

2) In addition, an EQP titration was performed. Two equivalencepoints have been found.

3) The arrows in the titration curve indicate two equivalencepoints due to the presence of at least two acids of differentstrength.

Literature:Application DL40RC No. 117.

Remarks

Blank determination (Meth. blv):R1 = QR1 is stored as auxiliary value H5

Acid value det. (Meth: 40012):R1 = (Q1 - H5)*C1/mC1 = 56.1

Calculation

Determination of the acid number of cosmetic creams


U. Büchi/P. SchauweckerAuthor

7


Results from endpoint titration to EPA = -310 mV (phenolphtalien colour change):

DL40RC:

*** 17-NOV-81 ***

PROV. 11321 1321IDENT. 81596SAMPLE NO. 2

*R * TAN 5.8836

STATISTICS:

N 2MEAN 5.9188STAND.DEV.% .84

Titration curve

Results

8

Method 40012 Acid No. Cosm. Cream Version 11-Dec-2001 10:00

Title Method ID . . . . . . . . . . . . . 40012 Title . . . . . . . . . . . . . . . Acid No. Cosm. Cream Date/time . . . . . . . . . . . . . 11-Dec-2001 10:00Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 1.0 Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 90EQP Titration Titrant . . . . . . . . . . . . . . KOH/EtOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.3 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 100 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . ml Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R2=(Q-H5)*C2/m Constant . . . . . . . . . . . . . . C2=M/z Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mg KOH/g Result name . . . . . . . . . . . . Acid No. Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Report Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

MethodMethod blv Blank value Version 11-Dec-2001 10:05

Title Method ID . . . . . . . . . . . . . blv Title . . . . . . . . . . . . . . . Blank value Date/time . . . . . . . . . . . . . 11-Dec-2001 10:05Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Volume Volume [mL] . . . . . . . . . . . 50.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 90EQP Titration Titrant . . . . . . . . . . . . . . KOH/EtOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.3 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 100 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Auxiliary value ID text . . . . . . . . . . . . . . Blindwert Formula . . . . . . . . . . . . . . H5=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

9

M230

Acidic / basic components

100 mL Sulphuric acid, H2SO4 ,c(1/2 H2SO4) = 0.5 mol/L

Sodium hydroxide, NaOHc(NaOH) = 0.25 mol/L


Method "back":H2SO4 + 2 NaOH = Na2SO4 + 2 H2O

Method 40013:Acidic/alkaline components


METTLER TOLEDO

Aqueous waste (after neutralization)Wastedisposal

Preparation and ProceduresBaking powder, 10 gUse 5 mL aliquots

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG111-SCIndication

Neutralizing Value of Baking Powder

1) 100 mL sulphuric acid c(1/2 H2SO4) = 0.5 mol/L are addedcarefully to the weighed sample and stirred during 10 min.

2) The sample solution is subsequently filtered. CO2 is thenremoved from the filtrate in an ultrasonic bath. (CO2 can also beremoved by heating the solution prior titration).

3) For the titration, 5 mL aliquot samples are taken.

Procedure:1) A known amount of sulphuric acid is added to the sample.2) Baking powder kan be either acidic or alkaline. Therefore, theresult in mmol/g can be negative or positive:

Negative result:Baking powder is alkaline (Sulphuric acid amount higher thanequivalent value of titrant)

Positive result:Baking powder is acidic (Sulphuric acid amount lower thanequivalent value of titrant)For a final result in %, multiply with M/(10*z), where M/z is theequivalent mass of the acidic or alkaline compound.

1) The method can be used for both alkaline and acidic bakingpowders.

2) The amount of sulphuric acid added before titration,expressed in mmol, is introduced as auxiliary value H6 in thetitrator.

3) The exact amount of sulphuric acid is determined by asimilar method using only 5 mL of sulphuric acid (see method"back"). In this way, it is not necessary to perform astandardization of the sulphuric acid solution.


Remarks

Method "back":R1=Q*C1 ; C1=1/z ; mmol H2SO4

R1 stored as aux. value H6

Method 40013 (sample deter.):R2=(H6-Q)*C2/m ; C2=1/zNeutral. value mmol/g

Calculation

Determination of the neutralizing value of baking powder by titration with sodium hydroxide.


K. Mooibroek/P. SchauweckerAuthor

10


DL40RC:

*** 20-NOV-81 ***

INPUT:WEIGHT 0.527IDENT. 85.09BLANK MEQ 2.5067

METHOD 118 1521IDENT. 85.09SAMPLE NO. 8

*R * /G .13275

STATISTICS:

N 8MEAN 0.12 /GSTAND.DEV.% 10.0

Titration curve

Results

11

Method 40013 Neutr.Value Version 11-Dec-2001 11:00

Title Method ID . . . . . . . . . . . . . 40013 Title . . . . . . . . . . . . . . . Neutr.Value Date/time . . . . . . . . . . . . . 11-Dec-2001 11:00Sample Sample ID . . . . . . . . . . . . . Baking Pwd. Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 5.0 Molar mass M . . . . . . . . . . . . 100.0 Equivalent number z . . . . . . . . 2 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10EQP Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.3 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . . 4.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 60 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . ml Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R2=(H6-Q)*C2/m Constant . . . . . . . . . . . . . . C2=1/z Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol/g Result name . . . . . . . . . . . . Neutral. value Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Report Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

MethodMethod back Back value Version 11-Dec-2001 11:05

Title Method ID . . . . . . . . . . . . . Back Title . . . . . . . . . . . . . . . Back value Date/time . . . . . . . . . . . . . 11-Dec-2001 11:05Sample Sample ID . . . . . . . . . . . . . H2SO4 Entry type . . . . . . . . . . . . . Volume Volume [mL] . . . . . . . . . . . 5.0 Molar mass M . . . . . . . . . . . . 98.08 Equivalent number z . . . . . . . . 2 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10EQP Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.25 Sensor . . . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.3 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . . 4.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 60 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=Q*C1 Constant . . . . . . . . . . . . . . C1=1/z Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . mmol H2SO4

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Auxiliary value ID text . . . . . . . . . . . . . . Back value Formula . . . . . . . . . . . . . . H6=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

12

M231

Acidic components

50 mL tetrahydrofuran

KOH in Ethanol:c(KOH) = 0.1 mol/L



METTLER TOLEDO


Preparation and ProceduresPolyester, 0.2-0.4 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Acid Number of Polyester

If needed, a blank value determination is performed. The blankvalue is stored as auxiliary value H7.

Remarks

Blank determination (Meth. blk):R1 = QR1 is stored as auxiliary value H7


Calculation

Determination of the acid number of polyester


R. Boehlen, MT-CHAuthor

13


METTLER TOLEDO DL58 Titrator V2.4 5121086246

Method 2 Säurezahl 05-04-2001 15:33 Measured 05-04-2001 15:44 User RB

ALL RESULTS


1 0.3113 g R1 = 26.78 mg/g Säurezahl R2 = 2.08 mL Verbrauch

Titration curve

Results

14

Method 2 Saeurezahl Version 05-04-2001 15:53

Title Method ID . . . . . . . . . . . . . 2 Title . . . . . . . . . . . . . . . Saeurezahl Date/time . . . . . . . . . . . . . 05-04-2001 15:33Sample Sample ID . . . . . . . . . . . . . Polyester Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.2 Upper limit [g] . . . . . . . . . 0.4 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 70 Time [s] . . . . . . . . . . . . . . 240EQP Titration Titrant . . . . . . . . . . . . . . KOH/EtOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.1 dV(max) [mL] . . . . . . . . . . 0.5 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . . 20.0 Recognition Threshold . . . . . . . . . . . . 500 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R=(Q-H7)*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg/g Result name . . . . . . . . . . . . Saeurezahl Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Verbrauch Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Report Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

MethodMethod blk Blindwert Version 05-04-2001 15:05

Title Method ID . . . . . . . . . . . . . blk Title . . . . . . . . . . . . . . . Blindwert Date/time . . . . . . . . . . . . . 05-04-2001 15:05Sample Sample ID . . . . . . . . . . . . . THF Entry type . . . . . . . . . . . . . Volume Volume [mL] . . . . . . . . . . . 50.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10EQP Titration Titrant . . . . . . . . . . . . . . KOH/EtOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.5 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . . 20.0 Recognition Threshold . . . . . . . . . . . . 500 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Auxiliary value ID text . . . . . . . . . . . . . . Blindwert Formula . . . . . . . . . . . . . . H7=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

15

M076

Free fatty acids

40 mL 1:1 ethanol:ether

KOH in ethanol:c(KOH) = 0.05 mol/L


R-COOH + OH- = R-COO- + H2O

1 additional burette drive DV901 additional burette DV1020100 mL beaker ME-101974Printer, Balance

METTLER TOLEDO


Preparation and ProceduresOil, fat, butter, 0.5-10 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Free Fatty Acid of Oil and Fat

1) For oil, fat and butter a 1:1 mixture of ether and ethanol isgenerally usedas a solvent. It can be added automatically with afunction DISPENSE.

2) To achieve a complete dissolution of the sample, anadditional stirring with higher stirrer speed during 1-2 minutes isused.

3) Calculations:The acid number of an oil or fat is the amount of of potassiumhydroxide in mg required to neutralize 1 g of the sample. Theresult is expressed as mg KOH/g sample or as percentage offree acidity:

Acid number AN = 5.61*a*t/m mg KOH/g

Free Fatty acid FFA = a*t*M/(100*m) %

M = Molecular mass of the fatty acid involved:M = 288 (oleic acid)M = 256 (palmitic acid, in palm oil)M = 200 (lauric acid, in palm kernel and coconut oils)M = 338 (eruca acid, in rape oil, rape fat)a = KOH consumption (mL)t =Titer (KOH)

1) The acid number is a measure of the decomposition bylipase enzyme of the glycerides in oil ands fats.Thedecomposition is accelerated by heat and light. Rancidity idue todecomposition is usually accompanied by free fatty acidformation.

2) Blank determination (method 076b):Acidic impurities in the solvent are taken into account by a blankvalue H8, or the solvent is neutralized before titration

3) Electrode conditioning:To ensure hydration of the membrane glass, the Dg113electrode is stoed over night in water. Before titraiton, clean theelectrode with solvent.

4) Butter and coconut fats: For a complete dissolution 5 minuteshigh speed stirring is required. After each sample, the fatty layeron the electrode must be removed by rinsing it with solvent. Thetitration curve of butter is flat. The threshold hs to lowered to 400mV.

5) Difficult samples:Samples can show a rather flat curve, and noise can appear.Theaddition of 1 mL 0.05 mol/L benzoic acid to the sample solvesthe problem.

Remarks

Blank determination (Meth. 076b):R1 = QR1 is stored as auxiliary value H8

Acid value det. (Meth: 076a):R1 = (Q1 - H8)*C1/mC1 = M/z

Calculation

Determination of the acid number of free fatty acids of oils, fats, and butter

Standard Benzoic acid

A. AichertAuthor

16


METTLER DL77 Titrator V3.1 Mettler-Toledo AG *114* Market Support Laboratory

Method 076a FFA in Oil and Fat 28-Sep-1994 12:18User dwMeasured 28-Sep-1994 16:16

RESULTS

No ID1 ID2 Sample amount and results

1/1 Thistle oil 6.444 g Weight m R1 = 0.477 mg KOH/g Acid Value 1/2 Thistle oil 6.447 g Weight m R1 = 0.481 mg KOH/g Acid Value 1/3 Thistle oil 6.448 g Weight m R1 = 0.482 mg KOH/g Acid Value 1/4 Thistle oil 6.442 g Weight m R1 = 0.481 mg KOH/g Acid Value 1/5 Thistle oil 6.445 g Weight m R1 = 0.482 mg KOH/g Acid Value 1/6 Thistle oil 6.444 g Weight m R1 = 0.477 mg KOH/g Acid Value

STATISTICS Number results R1 n = 6 Mean value x = 0.480 mg KOH/g Acid Value Standard deviation s = 0.0022 mg KOH/g Acid Value Rel. standard deviation srel = 0.449 % Outlier test: no outliers!

Titration curve

Results

17

Method 076a FFA in Oil and Fat Version 28-Sep-1994 12:18

Title Method ID . . . . . . . . . . . . . 076a Title . . . . . . . . . . . . . . . FFA in Oil and Fat Date/time . . . . . . . . . . . . . 28-Sep-1994 12:18Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.5 Upper limit [g] . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . Thistle Molar mass M . . . . . . . . . . . . 56.11 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 0 Time [s] . . . . . . . . . . . . . . 0Dispense Titrant . . . . . . . . . . . . . . EtOH/Ether Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 40.0Stir Speed [%] . . . . . . . . . . . . . 70 Time [s] . . . . . . . . . . . . . . 60Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 5Titration Titrant . . . . . . . . . . . . . . KOH/EtOH Concentration [mol/L] . . . . . . . 0.05 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mV] . . . . . . . . . 0.5 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.01 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . 1.5 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 1000.0 Maximum volume [mL] . . . . . . . 5.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Acid Value Formula . . . . . . . . . . . . . . R=(Q-H8)*C/m Constant . . . . . . . . . . . . . . C=M/z Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod 076b FFA in Oil and Fat / Blank Version 28-Sep-1994 11:33

Title Method ID . . . . . . . . . . . . . 076b Title . . . . . . . . . . . . . . . FFA in Oil and Fat / Blank Date/time . . . . . . . . . . . . . 28-Sep-1994 11:33Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.5 Upper limit [g] . . . . . . . . . 5.0 ID1 . . . . . . . . . . . . . . . . Blank Molar mass M . . . . . . . . . . . . 56.11 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 0 Time [s] . . . . . . . . . . . . . . 0Dispense Titrant . . . . . . . . . . . . . . EtOH/Ether Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 40.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 5Titration Titrant . . . . . . . . . . . . . . KOH/EtOH Concentration [mol/L] . . . . . . . 0.05 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 10.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.005 dV(max) [mL] . . . . . . . 0.04 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . 1.5 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 800.0 Maximum volume [mL] . . . . . . . 0.3 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank FFA Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . FFA Blank Formula . . . . . . . . . . . . . . H8=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

18

M086

Epoxide end groups

50 mL Dichloromethane:glacial aceticacid 4:1 ;2 g Tetra-n-butylammonium iodide

Perchloric acid in acetic acid, HClO4

c(HClO4) = 0.1 mol/L


1 additional burette drive DV901 additional burette DV1020100 mL glass beaker ME-101974Printer, Balance

METTLER TOLEDO

Halogenated, organic solvent wasteWastedisposal

Preparation and ProceduresAralditRM powdersSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Epoxide Values

1) Epoxide resins are dissolved in a mixture consisting of fourparts dichloromethane (water content <0.02%) and one partglacial acetic acid (water content <0.5%).

2) The resin is weighed and dissolved in 50 mL solventmixture. The sample size is selected according to the epoxideequivalent weight. It is selected in order to get a titrantconsumption in the order of 10-20 mL.

3) The solution can be warmed up to 50°C to improvedissolution, and cooled to room temperature before startingtiration. Generally, solid resins are completely dissolved after tenminutes stirring time (see method 086).

4) 2 g Tetra-n-butylammonium iodide are added to the samplesolution, and the titration method is started.

1) This method describes the determination of epoxide valuebased on to DIN 53188 and ASTM D1652-80. Epoxide resinsare resins which contains epoxide end goups.

2) Water in the solvent can affect the results. Therefore, onlyanhydrous reagents should be used.

3) This application can not be used for epoxide resinscontaining alkaline groups.

4) Perchloric acid reacts stoichiometrically with epoxide endgroups.

5) Calculations:The epoxide equivalent weight (EEW) is the amount of epoxideresin in g which contains 16 g of oxigen bound as epoxide:EEM = m * 1000 / Q g/Mol

The epoxide value (EV) indicates the amount-of-substance ofepoxide groups in 100 g of an epoxide resin:EV = 100 / EEM Mol/100 g sample

The content of oxirane oxigen in % = 1.6*Q/m

Literature:ASTM D 1652-80, DIN 53188

Remarks

Blank determination (method 086b):R1 = Q ; mmolR1 is stored as auxiliary value H9.Epoxide value det. (Method 086a):R1 = (Q-H9)/(10*m) ; mg Mol/100gR2 = (m*1000)/(Q1-H9) ; g/MolR3 = (Q1-H9)*1.6/m ; %

Calculation

Determination of the epoxide values in resins according to ASTM D1652-80 and DIN 53188

Standard Tris(hydroxymethyl)aminomethane

K. MooibroekAuthor

19


METTLER DL67 Titrator V3.1 Mettler-Toledo AG DL67(1) Market Support Laboratory

Method 086a Epoxy Content 09-Mar-1994 15:28User K.M.Measured 10-Mar-1994 11:10

RESULTS LAST SAMPLE


1/2 Polymer 2.0734 g Weight m R1 = 0.069 Mol/100g Epoxy Content R2 = 1439.246 g/Mol Epoxide Eq.W. R3 = 1.112 % Oxirane O 2

No. Probe Einwaage (g) n Epoxide equiv. Epoxide Oxiran srel weight value oxygen (g) (g/mol) (mol/100 g) (%) (%)

1 Araldit 2 0.4973 - 0.5562 6 1482.188 0.068 1.084 6.632

2 Araldit 9 2.0 - 2.5053 4 1440.431 0.069 1.111 0.1062

Titration curve

Results

20

Method 086a Epoxy Content Version 09-Mar-1994 15:28

Title Method ID . . . . . . . . . . . . . 086a Title . . . . . . . . . . . . . . . Epoxy Content Date/time . . . . . . . . . . . . . 09-Mar-1994 15:28Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 2.0 ID1 . . . . . . . . . . . . . . . . Polymer Molar mass M . . . . . . . . . . . . 0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 75 Time [s] . . . . . . . . . . . . . . 600Titration Titrant . . . . . . . . . . . . . . HClO4

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.1 dt [s] . . . . . . . . . . . 5.0 t(min) [s] . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 75.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . -1000 Limit B . . . . . . . . . . . 1000 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Epoxy Content Formula . . . . . . . . . . . . . . R1=(Q1-H9)/(10*m) Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Mol/100g Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . Epoxide Eq.W. Formula . . . . . . . . . . . . . . R1=(m*1000)/(Q1-H9) Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . g/Mol Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . Oxirane O2

Formula . . . . . . . . . . . . . . R3=(Q1-H9)*1.6/m Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer Short-form method . . . . . . . . . Yes All results . . . . . . . . . . . . Yes

MethodMethod 086b Blank Version 17-Dec-2001 10:15

Title Method ID . . . . . . . . . . . . . 086a Title . . . . . . . . . . . . . . . Blank Date/time . . . . . . . . . . . . . 17-Dec-2001 10:15Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 2.0 ID1 . . . . . . . . . . . . . . . . Polymer Molar mass M . . . . . . . . . . . . 0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 15Titration Titrant . . . . . . . . . . . . . . HClO4

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.005 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.1 dt [s] . . . . . . . . . . . 5.0 t(min) [s] . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 75.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . -1000 Limit B . . . . . . . . . . . 1000 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Epoxide Blank Formula . . . . . . . . . . . . . . H9=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

21

M232

Epoxide end groups

50 mL 0.4 mol/L TEAB solution(Tetraethylammonium bromide inglacial acetic acid), M(TEAB)= 210.16

Perchloric acid in acetic acid, HClO4

c(HClO4) = 0.1 mol/L


100 mL glass beaker ME-101974Printer, Balance

METTLER TOLEDO

Halogenated, organic solvent wasteWastedisposal

Preparation and Procedures0.1 g2,3-epoxypropylene-phenyl ether, 99%

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Epoxide Value of 2,3-Epoxypropylene-Phenyl Ether

1) 0.1 g sample are dissolved in 50 mL 0.4 mol/L TEABsolution

2) TEAB: tetraethylammonium bromide

1) Water in the solvent can affect the results. Therefore, onlyanhydrous reagents should be used.

2) Perchloric acid reacts stoichiometrically with epoxide endgroups.

3) After each meausrement the electrode was placed in water forapproximately 5 minutes.

Remarks

Blank determination (method vsb):R1 = Q ; mmolR1 is stored as auxiliary value H10.Epoxide value det. (Method vsa):R1 = (Q-H10)*C/m ; C=1/z ; mol/kgR2 = VEQ ; mLR3 = 1000/R1 ; Epoxide value

Calculation

Determination of the epoxide value by titration with HClO4

Standard Tris(hydroxymethyl)aminomethane

Viola Mueller-SchindlerAuthor

22


METTLER TOLEDO DL58 Titrator V2.0 Titrations-Kurs 20.-29. Mai 1997

Method vsa Epoxid Bestimmung 27-Mai-1997 14:58 Measured 27-Mai-1997 15:59 User VS

ALL RESULTS


1 0.116 g R1 = 6.6592 mol/kg Gehalt R2 = 7.7246 mL R3 = 150.2 Epoxyd Wert 2 0.0955 g R1 = 6.6948 mol/kg Gehalt R2 = 6.3935 mL R3 = 149.4 Epoxyd Wert 3 0.1035 g R1 = 6.6692 mol/kg Gehalt R2 = 6.9026 mL R3 = 149.9 Epoxyd Wert 4 0.0964 g R1 = 6.6767 mol/kg Gehalt R2 = 6.4363 mL R3 = 149.8 Epoxyd Wert

STATISTICS Number results R1 n = 4 Mean value x = 6.6750 mol/kg Gehalt Standard deviation s = 0.01504 mol/kg Gehalt Rel. standard deviation srel = 0.225 %STATISTICS Number results R2 n = 4 Mean value x = 6.8643 mL Standard deviation s = 0.61818 mL Rel. standard deviation srel = 9.006 %

Titration curve

Results

23

Method vsa Epoxid Bestimmung Version 27-Mai-1997 14:58

Title Method ID . . . . . . . . . . . . . Title . . . . . . . . . . . . . . . Epoxid Bestimmung Date/time . . . . . . . . . . . . . 27-Mai-1997 14:58Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 5.0 Molar mass M . . . . . . . . . . . . 1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 120EQP Titration Titrant . . . . . . . . . . . . . . HClO4 Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . Yes Volume [mL] . . . . . . . . . . . 1.0 Wait time [s] . . . . . . . . . . 0 Titrant addition . . . . . . . . . . Incremental dV [mL] . . . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 170 Steepest jump only . . . . . . . Yes Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination Maximum volume [mL] . . . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R=(Q-H10)*C/m Constant . . . . . . . . . . . . . . C=1/z Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mol/kg Result name . . . . . . . . . . . . Gehalt Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R3=1000/R1 Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 1 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Epoxid Wert Statistics . . . . . . . . . . . . . NoReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

MethodMethod vsb Blank Version 27-Mai-1997 14:30

Title Method ID . . . . . . . . . . . . . vsb Title . . . . . . . . . . . . . . . Blank Date/time . . . . . . . . . . . . . 27-Mai-1997 14:30Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Volume Volume [mL] . . . . . . . . . . . 50.0 Molar mass M . . . . . . . . . . . . 1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 20EQP Titration Titrant . . . . . . . . . . . . . . HClO4 Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Incremental dV [mL] . . . . . . . . . . . . . 0.02 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 170 Steepest jump only . . . . . . . Yes Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination Maximum volume [mL] . . . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . No Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Auxiliary value ID text . . . . . . . . . . . . . . Blindwert Formula . . . . . . . . . . . . . . H10=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

24

M087

Carbon-Carbon double bounds

50 mL solvent mixture

Bromide-Bromate, Br-/BrO3-

c(Br2) = 0.05 mol/L

DL70ES, DL77

Bromine generation:BrO3

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

Bromine addition to C=C double bond:R-CH=CH-R2 + Br2 = R-CHBr-CHBr-R2

1 additional burette drive DV90Thermostatable vessel ME-23517DT120 Temperature sensor (Pt100)AT261 balance, Printer

METTLER TOLEDO

Chlorinated organic solventsWastedisposal

Preparation and ProceduresPetroleum distillates and aliphaticolefins

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SC with DK102A, cables Ban.-SC 51108061, LEMO-SC 89601

Indication

Bromine Number of Petroleum Distillates and Aliphatic Olefins

1) Solvent mixture according to ASTM D1159-89:714 mL glacial acetic acid, 134 mL 1,1,1-trichloroethane134 mL methanol, and 18 mL 1+5 H2SO4 (16%)

Preparation of 1+5 H2SO4 solution:Add 1 volume concentrated H2SO4 (specific gravity 1.84) to 5volumes deionized water.

2) Cool the solvent to 0-5°C before starting titration by settingthe temperature of the thermostate.

3) The DK102A polrization current is set to 0.5 µA, and it isconnected to sensor input 1. Voltametric end point indicationallows a fast and accurate deterimantion. At the appearance ofunreacted bromine a significant potential change is monitored.

4)The commercially available Bromide-Bromate solution is usedas a titrant. It is stable and does not need a standardization. Ifnecessary (e.g. by home-made titrant) reagents and titrant arechecked by titrating standards as given in ASTM D1159-89.

5) A blank is determined for every new batch of solvent mixture(Method 087B)

1) The bromine number is the number of grams of brominewhich react completely with 100 g of the sample under theconditions indicated by the standard ASTM 1159-89.

It gives the quantity of bromine reactive components, and it alsocharacterizes the degree of unsaturation of the sample, basedonly the addition reaction.

2) By choosing the appropriate reaction conditions -i.e. thecomposition of the solvent and a reaction temperature between0-5°C- only the additoon reaction takes place, whilesubstitution and oxidation reactions are suppressed.

3) Method 087A is especially designed for fast voltametric endpoint titration with continuous titrant addtion according to ASTMD1159-89 (delay time 30 s, increment 0.1 mL)

Literature:ASTM D1159-89, IP130/85

Remarks

Blank determination (Meth. 087B):R1 = QR1 is stored as aux. value H11

Bromine No. det. (Meth: 087A):R1 = (Q-H11)*15.98/m

Calculation

Bromine number determinations of petroleum distilates according to ASTM D1159-89 and IP130/85

Standard


25


No. Sample Weight n Bromine srel time Number (g) (g/100g) (%) (min)

1 Gasoline A 0.2165 6 55.4 3.03 3

2 Gasoline B 0.2 - 0.5 8 25.9 1.56 4

3 1-Decene 0.03296 6 106 1.82 8

4 Cyclopentene 0.03033 6 232 1.43 2

5 Cyclohexene 0.0518 6 198 2.57 3

Titration curve

Results

26

Method 087A Bromine number Version 25-Oct-1993 4:07 pm

Title Method ID . . . . . . . . . . . . . 087A Title . . . . . . . . . . . . . . . Bromine number Date/time . . . . . . . . . . . . . 25-Oct-1993 4:07 pmSample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 2.0 ID1 . . . . . . . . . . . . . . . . Bromine Molar mass M . . . . . . . . . . . . 159.8 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . TEMP AStir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 120Temperature Sensor . . . . . . . . . . . . . . . TEMP A Unit of meas. . . . . . . . . . . . °C dT [°C,°F,K] . . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . . . . 2.0 t(min) mode . . . . . . . . . . . . T < set value Set value [°C,°F,K] . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . . . 600.0Titration Titrant . . . . . . . . . . . . . . Bromide-Bromate Concentration [mol/L] . . . . . . . 0.05 Sensor . . . . . . . . . . . . . . . DK102A/DM143 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EP Titrant addition . . . . . . . . Continuous Control band [mV,pH,...] . . . 3000 Delay [s] . . . . . . . . . . 30 dV(min) [mL] . . . . . . . . . 0.02 End point mode . . . . . . . . . EPA Potential [mV,pH,...] . . . . -150.0 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 20.0Calculation Result name . . . . . . . . . . . . Bromine Number Formula . . . . . . . . . . . . . . R=(Q-H11)*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Result unit . . . . . . . . . . . . g Br2/100g Decimal places . . . . . . . . . . . 2Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod 087B Bromine Number:Blank Version 21-Oct-1993 6:31 pm

Title Method ID . . . . . . . . . . . . . 087B Title . . . . . . . . . . . . . . . Bromine Number:Blank Date/time . . . . . . . . . . . . . 21-Oct-1993 6:31 pmSample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . Blank Molar mass M . . . . . . . . . . . . 159.8 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . TEMP AStir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 120Temperature Sensor . . . . . . . . . . . . . . . TEMP A Unit of meas. . . . . . . . . . . . °C dT [°C,°F,K] . . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . . . . 2.0 t(min) mode . . . . . . . . . . . . T < set value Set value [°C,°F,K] . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . . . 600.0Titration Titrant . . . . . . . . . . . . . . Bromide-Bromate Concentration [mol/L] . . . . . . . 0.05 Sensor . . . . . . . . . . . . . . . DK102A/DM143 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EP Titrant addition . . . . . . . . Continuous Control band [mV,pH,...] . . . 3500 Delay [s] . . . . . . . . . . 30 dV(min) [mL] . . . . . . . . . 0.001 End point mode . . . . . . . . . EPA Potential [mV,pH,...] . . . . -150.0 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 5.0Calculation Result name . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . R1=H11 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol/50 mL Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Blank value Bromine Formula . . . . . . . . . . . . . . H11=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

27

M233

Carbon-Carbon double bounds(Cyclohexene)

50 mL solvent mixture

Bromide-Bromate, Br-/BrO3-

c(Br2) = 0.05 mol/L

DL38DL50Graphix, DL53/55/58 with KFOption and DV705 KF titration stand

Bromine generation:BrO3

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

Bromine addition to C=C double bond:R-CH=CH-R + Br2 = R-CHBr-CHBr-R

Thermostatable vessel ME-51 107 497AT261 balance, Printer

METTLER TOLEDO

Chlorinated organic solventsWastedisposal

Preparation and ProceduresCyclohexene in glacial acetic acid,5-10 ppm

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM143-SC, or Pt885-NS-S7/105(ME-59 904 435)

Indication

Low Bromine Index Determination of a Standard Solution

1) Solvent mixture according to ASTM D2710-89:714 mL glacial acetic acid, 134 mL 1,1,1-trichloroethane134 mL methanol, and 18 mL 1+5 H2SO4 (16%)

Preparation of 1+5 H2SO4 solution:Add 1 volume concentrated H2SO4 (specific gravity 1.84) to 5volumes deionized water.

2) Cool the solvent to 0-5°C before starting titration by settingthe temperature of the thermostate.

3) Voltametric end point indication allows a fast and accuratedeterimantion. At the appearance of unreacted bromine asignificant potential change is monitored.

4) The commercially available Bromide-Bromate solution isused as a titrant. It is stable and does not need astandardization. If necessary (e.g. by home-made titrant)reagents and titrant are checked by titrating standards as givenin ASTM D2710-99.

5) A blank is determined for every new batch of solvent mixture(Method 111)

1) The bromine index is the number of milligrams of brominewhich react completely with 100 g of the sample under theconditions indicated by the standard ASTM 2710-99.

It gives the quantity of bromine reactive components, and it alsocharacterizes the degree of unsaturation of the sample, basedonly the addition reaction.

2) By choosing the appropriate reaction conditions -i.e. thecomposition of the solvent and a reaction temperature between0-5°C- only the addition reaction takes place, while substitutionand oxidation reactions are suppressed.

3) For very low bromine index values the platinum double ringelectrode Pt885-NS-S7/105 (ME-59 904 435) was found to bevery suitable. In this case, it is recommended to replace theDM143 electrode with the Pt885 electrode.

Literature:ASTM D2710-99, IP299/92

Remarks

Blank determination (Meth. 111):R1 = VEQ , stored as blank

Bromine Index. det. (Meth. 112):R1 =(Consumption-Blank)*Conc*15980/m

Calculation

Bromine index determinations of a standard solution according to ASTM D2710-99 and IP299/92

Standard

Cosimo De CaroAuthor

28


METTLER TOLEDO DL38 V1.2-------------------------------------------------------------------------------Method: 112 Br. Index 20-11-2000 15:37User: Cosimo Measured: 22-11-2000 9:35File: C:\COSIMO\RECKB112.008Printed: 20-12-2001 10:41-------------------------------------------------------------------------------

Calculation factor f1 = 1.0000Calculation factor f2 = 1.0000Calculation factor f3 = 0.0500

RESULTS Br No. determination

No. Sample-ID Sample size and results

1 10mL4.724E-5g/mL 10.5 g Bromine index = 9.09 R2 = 0.292 mL R3 = 0.0146 mmol




STATISTICS Bromine index n = 4 Mean value = 9.11 Std. devn = 0.896352 srel = 9.836 %STATISTICS No. results R3 n = 4 Mean value = 0.0115 mmol Std. devn = 0.002350 mmol srel = 20.523 %

Titration curve

Results

29

Method . . . . . . . . . . . . . . . . . . . . . 112 Title . . . . . . . . . . . . . . . . . . . . Br. Index Version . . . . . . . . . . . . . . . . . . . 20-11-2000 15:37 Author . . . . . . . . . . . . . . . . . . . CDCSample parameters ID . . . . . . . . . . . . . . . . . . . . . Request Type . . . . . . . . . . . . . . . . . . . . Mass Minimum [g] . . . . . . . . . . . . . . . . . 8.0000 Maximum [g] . . . . . . . . . . . . . . . . . 30.0000 Entry . . . . . . . . . . . . . . . . . . . . BeforeSpeed [%] . . . . . . . . . . . . . . . . . . . 40Mix time [s] . . . . . . . . . . . . . . . . . . 300Titrant . . . . . . . . . . . . . . . . . . . . Br-/BrO3-Predisp.[mL] . . . . . . . . . . . . . . . . . . 0.0000Wait time [s] . . . . . . . . . . . . . . . . . 0Control parameters Current [uA] . . . . . . . . . . . . . . . . 1 End point [mV] . . . . . . . . . . . . . . . 150 dVmin [uL] . . . . . . . . . . . . . . . . . 1.0 dVmax [uL] . . . . . . . . . . . . . . . . . 20.0 dVmax factor [%] . . . . . . . . . . . . . . 100 Start . . . . . . . . . . . . . . . . . . . . CautiousTermination param. Max. time [s] . . . . . . . . . . . . . . . . 6000 Delay [s] . . . . . . . . . . . . . . . . . . 30 Vmax [mL] . . . . . . . . . . . . . . . . . . 20.000Blank [mmol] . . . . . . . . . . . . . . . . . . RequestCalculation 1 R1 = . . . . . . . . . . . . . . . . . . . . x [Brindex]*f1 f1 = . . . . . . . . . . . . . . . . . . . . 1.0000 Unit Decimal places . . . . . . . . . . . . . . . 2 Statistics . . . . . . . . . . . . . . . . . Yes Max. srel [%] . . . . . . . . . . . . . . . . 0.00Calculation 2 R2 = . . . . . . . . . . . . . . . . . . . . x [mL]*f2 f2 = . . . . . . . . . . . . . . . . . . . . 1.0000 Unit . . . . . . . . . . . . . . . . . . . . mL Decimal places . . . . . . . . . . . . . . . 3 Statistics . . . . . . . . . . . . . . . . . No Max. srel [%] . . . . . . . . . . . . . . . . 0.00Calculation 3 R3 = . . . . . . . . . . . . . . . . . . . . x [mL]*f3 f3 = . . . . . . . . . . . . . . . . . . . . 0.0500 Unit . . . . . . . . . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . . . . . 4 Statistics . . . . . . . . . . . . . . . . . Yes Max. srel [%] . . . . . . . . . . . . . . . . 0.00Report Output . . . . . . . . . . . . . . . . . . . Computer

Method

Method . . . . . . . . . . . . . . . . . . . . . 111 Title . . . . . . . . . . . . . . . . . . . . Blank Br.Ind Version . . . . . . . . . . . . . . . . . . . 20-11-2000 15:32 Author . . . . . . . . . . . . . . . . . . . CDCSample parameters ID . . . . . . . . . . . . . . . . . . . . . Request Type . . . . . . . . . . . . . . . . . . . . Fixed volume Density [g/mL] . . . . . . . . . . . . . . . 1.000 Volume [mL] . . . . . . . . . . . . . . . . . 55Speed [%] . . . . . . . . . . . . . . . . . . . 40Mix time [s] . . . . . . . . . . . . . . . . . . 300Titrant . . . . . . . . . . . . . . . . . . . . Br-/BrO3-Predisp.[mL] . . . . . . . . . . . . . . . . . . 0.0000Wait time [s] . . . . . . . . . . . . . . . . . 0Control parameters Current [uA] . . . . . . . . . . . . . . . . 1 End point [mV] . . . . . . . . . . . . . . . 150 dVmin [uL] . . . . . . . . . . . . . . . . . 1.0 dVmax [uL] . . . . . . . . . . . . . . . . . 5.0 dVmax factor [%] . . . . . . . . . . . . . . 100 Start . . . . . . . . . . . . . . . . . . . . CautiousTermination param. Max. time [s] . . . . . . . . . . . . . . . . 6000 Delay [s] . . . . . . . . . . . . . . . . . . 30 Vmax [mL] . . . . . . . . . . . . . . . . . . 5.000Blank [mmol] . . . . . . . . . . . . . . . . . . 0Calculation 1 R1 = . . . . . . . . . . . . . . . . . . . . x [mL]*f1 f1 = . . . . . . . . . . . . . . . . . . . . 0.0500 Unit . . . . . . . . . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . . . . . 4 Statistics . . . . . . . . . . . . . . . . . Yes Max. srel [%] . . . . . . . . . . . . . . . . 0.00Calculation 2 R2 = . . . . . . . . . . . . . . . . . . . . x [mL]*f2 f2 = . . . . . . . . . . . . . . . . . . . . 1.0000 Unit . . . . . . . . . . . . . . . . . . . . mL Decimal places . . . . . . . . . . . . . . . 3 Statistics . . . . . . . . . . . . . . . . . Yes Max. srel [%] . . . . . . . . . . . . . . . . 0.00Calculation 3Report Output . . . . . . . . . . . . . . . . . . . Computer

30

M090

Saponifiable esterified acids

Toluene, 50 mLEthanolic KOH, 20 mL c(KOH)=0.5 M

Hydrochloric acid in isopropanolc(HCl) = 0.5 mol/L

DL67/70ES/77,DL50 Graphix, DL53/55/58

R1-CO-O-R2 + OH- = R1-COO- +HO-R2

Reflux condenser, water baththermostat, 100 mL Erlenmeyer beaker,AT261 Balance, printer, DL55/58,DL70ES/77: addi. burettes

METTLER TOLEDO

Organic solvents (halogenated or not)Wastedisposal

Preparation and ProceduresResin, 3 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Determination of Saponification Value

Sample preparation1) The sample is dissolved in 50 mL toluene in a 100 mLErlenmeyer beaker.Note: The Erlenmeyer beaker must be fit the reflux condenser.2) 20 mL 0.5 ml/L KOH are added to the sample solution.3) Boil under reflux condition for 30 minutes.4) Cool down the sample solution to room temperature beforestarting titration.

Boiling under reflux condiction:1) The boiling time is crucial2) Use organic solvents (or solvent mixtures) which do notundergo saponification and other side reactions: methanol,ethanol, toluene, isopropanol, ethylene glycol. Thesaponification temperature is determined by the solvent used.3) If necessary: The reaction of the sample with carbon dioxideis preventeed by flushing the titration vessel and refluxcondenser with nitrogen gas.

Titration:The saponification value is determined by back-titration with HClafter saponification reaction. This is achieved by addition of aknown amount of KOH and subsequent reflux boiling. UnreactedKOH is then determined by titration with HCl.

The saponification value is a reference value for the amount ofsaponified acidic components present in the sample. Itcorresponds to the amount of KOH (in mg) used for thesaponification.

The described procedure is used for the determination of thecontent of esterified acids in products such as solvents, oils,fats, resins, fatty acids as well as softeners used in the polymerindustry. Free acidic as well as anhydrous compounds are alsoincluded.

Two titration methods are used in this analysis: a blank and asample titration. The blank value is stored as auxiliary valueH12 in the titrator.

Literature:1. DIN 53401, 51559, 534042. Schweizerisches Lebensmittelbuch, 5th edition,Eidgenössische Druck- und Materialzentrale, Bern, 19933. Application M618, Mettler-Toledo Application brochure 24,ME-51725054

Remarks

Blank (Method 090B):R1=Q ; mmolStored as auxiliary value H12

Saponification value (Method 090A):R1=(H12-Q)*(C1/m)C1=56.1 ; mg KOH/g

Calculation

Determination of saponification value in resins according to DIN 53401

Standard KHP for KOH, THAM for HCl


31


METTLER DL67 Titrator V3.1 Mettler-Toledo AG DL67 (1) Market Support Laboratory

Method 090A Saponification Value 06-Apr-1994 11:42User K.M.Measured 06-Apr-1994 13:31

RESULTS


1/1 Saponif. Resin 1 2.902 g Weight m R1 = 157.266 mg KOH/g Saponif.value 1/2 Saponif. Resin 2 2.9075 g Weight m R1 = 159.202 mg KOH/g Saponif.value 1/3 Saponif. Resin 3 2.8983 g Weight m R1 = 158.912 mg KOH/g Saponif.value 1/4 Saponif. Resin 4 2.9696 g Weight m R1 = 155.148 mg KOH/g Saponif.value 1/5 Saponif. Resin 5 2.9056 g Weight m R1 = 158.750 mg KOH/g Saponif.value 1/6 Saponif. Resin 6 2.902 g Weight m R1 = 159.590 mg KOH/g Saponif.value

STATISTICS Number results R1 n = 6 Mean value x = 158.144 mg KOH/g Saponif.value Standard deviation s = 1.668318 mg KOH/g Saponif.value Rel. standard deviation srel = 1.055 % Outlier test: no outliers!

Titration curve

Results

32

Method 090A Saponification Value Version 06-Apr-1994 11:42

Title Method ID . . . . . . . . . . . . . 090A Title . . . . . . . . . . . . . . . Saponification Value Date/time . . . . . . . . . . . . . 06-Apr-1994 11:42Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 20.0 ID1 . . . . . . . . . . . . . . . . Saponif. Molar mass M . . . . . . . . . . . . 0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . HCl Concentration [mol/L] . . . . . . . 0.5 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.0 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 250.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . -500 Limit B . . . . . . . . . . . +500 Maximum volume [mL] . . . . . . . 40.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Saponif.value Formula . . . . . . . . . . . . . . R1=(H12-Q1)*(C1/m) Constant . . . . . . . . . . . . . . C1=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod 090B Saponification, Blank Version 30-Mar-1994 13:46

Title Method ID . . . . . . . . . . . . . 090B Title . . . . . . . . . . . . . . . Saponification, Blank Date/time . . . . . . . . . . . . . 30-Mar-1994 13:46Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 20.0 ID1 . . . . . . . . . . . . . . . . Saponif. Molar mass M . . . . . . . . . . . . 0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . HCl Concentration [mol/L] . . . . . . . 0.5 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 12.0 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 500.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . -500 Limit B . . . . . . . . . . . +500 Maximum volume [mL] . . . . . . . 40.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Saponification Formula . . . . . . . . . . . . . . H12=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

33

M091

Hydroxyl groups

Catalyst solution:see preparation and proceduresAcetylation mixture:see preparation and procedures

Potassium hydroxide in methanol,c(KOH) = 0.5 mol/L(A second burette is used for water)

DL70ES/77,DL55+, DL58

Acetylation:

AT261 Balance, printerDL55/58, DL70ES/77:two additional burettes, ev. 1 DU200

METTLER TOLEDO

Aromatic organic solvents Wastedisposal

Preparation and ProceduresTrimethylolpropane(3-ethyl-2-(Hydroxymethyl)-1,3-propanediol)

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Determination of Hydroxyl Value

The sample is dissolved in a mixture of 25 mL catalyst solutionand 3 mL acetylation mixture. The acetylation mixture can beadded either by pipette/dosing unit, or using a burette.

Catalyst solution:12 g 4-Dimethylaminopyridine in 1 L DMF(DMF = N,N-Dimethylformamide),Acetylation mixture:250 mL acetic acid anhydride with 770 mL DMF

1) The acetylation reaction is catalysed by 4-dimethyl aminepyridine. This reaction takes place during the first stirringfunction. The stirring time must be adapted to the speed ofacetylation reaction. The dosing precision of the acetylationmixture also determines the overall accuracy of the analysis.Note: Water affects acetylation reaction.

2) After completion of acetylation water is addded to the samplemixture to hydrolize excess of acetic acid anhydride which is notused for the acetylation. The reaction time is defined in thesecond stirring function.

3) As a result, acetic acid is formed which is then back-titratedwith methanolic KOH solution.

The hydroxyl value is a reference number used to characterizepolyoles. It is expressed as the amount of KOH in mg toneutralize the consumed equivalent amount of acetic acid usedfor the acetylation of 1 g of sample.

Two titration methods are used in this analysis: a blank and asample titration. The blank value is stored as auxiliary valueH13 in the titrator.

Literature:1. DIN 53240, ASTM 2849(without refluxing at elevated temperature of sample/mixturesolution).

Remarks

Blank (Method 091B):R1 = Q1 ; mmolStored as auxiliary value H13

Hydroxyl value (Method 091A):R1 = (H13-Q)*(C1/m)C1 = 56.1 ; mg KOH/g

Calculation

Determination of hydroxyl value according to DIN 53240

Standard KHP


34


METTLER DL67 Titrator V3.1 Mettler-Toledo AG DL67 (1) Market Support Laboratory

Method 091A Hydroxyl Number, Sample 20-Jul-1994 11:32User K.M.Measured 20-Jul-1994 17:41

RESULTS


1/1 Sample 3779 0.5006 g Weight m R1 = 536.64 mg KOH/g Hydroxyl No. 1/2 Sample 3779 0.5006 g Weight m R1 = 665.83 mg KOH/g Hydroxyl No. 1/3 Sample 3779 0.5006 g Weight m R1 = 665.96 mg KOH/g Hydroxyl No. 1/4 Sample 3779 0.5006 g Weight m R1 = 654.04 mg KOH/g Hydroxyl No. 1/5 Sample 3779 0.5006 g Weight m R1 = 655.31 mg KOH/g Hydroxyl No. 1/6 Sample 3779 0.5006 g Weight m R1 = 608.25 mg KOH/g Hydroxyl No.

STATISTICS Number results R1 n = 6 Mean value x = 631.01 mg KOH/gHydroxyl No. Standard deviation s = 50.94823 mg KOH/gHydroxyl No. Rel. standard deviation srel = 8.074 %

Outlier test : sample No. 1/1, 1/6 Number results R1 n = 4 Mean value x = 660.29 mg KOH/gHydroxyl No. Standard deviation s = 6.502444 mg KOH/gHydroxyl No. Rel. standard deviation srel = 0.985 %

Titration curve

Results

35

Method 091A Hydroxyl Number, Sample Version 20-Jul-1994 11:32

Title Method ID . . . . . . . . . . . . . 091A Title . . . . . . . . . . . . . . . Hydroxyl Number, Sample Date/time . . . . . . . . . . . . . 20-Jul-1994 11:32Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 20.0 ID1 . . . . . . . . . . . . . . . . Sample Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 900Dispense Titrant . . . . . . . . . . . . . . Deionised water Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 300Titration Titrant . . . . . . . . . . . . . . KOH (MeOH) Concentration [mol/L] . . . . . . . 0.5 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 15.0 Threshold . . . . . . . . . . . . 250.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . 0 Limit B . . . . . . . . . . . -600 Maximum volume [mL] . . . . . . . 50.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Hydroxyl No. Formula . . . . . . . . . . . . . . R1=(H13-Q1)*(C1/m) Constant . . . . . . . . . . . . . . C1=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 2Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod 091B Hydroxyl number, Blank Version 23-Jun-1994 8:35

Title Method ID . . . . . . . . . . . . . 091B Title . . . . . . . . . . . . . . . Hydroxyl number, Blank Date/time . . . . . . . . . . . . . 23-Jun-1994 8:35Sample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 3.0 ID1 . . . . . . . . . . . . . . . . Blank Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 900Dispense Titrant . . . . . . . . . . . . . . Deionised water Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 300Titration Titrant . . . . . . . . . . . . . . KOH (MeOH) Concentration [mol/L] . . . . . . . 0.5 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 20.0 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 15.0 Threshold . . . . . . . . . . . . 500.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . 0 Limit B . . . . . . . . . . . -600 Maximum volume [mL] . . . . . . . 50.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . R1=Q1 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 2Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Blank (acetylation) Formula . . . . . . . . . . . . . . H13=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

36

M234

Hydroxyl groups

Ethanol:Toluene 1:1

KOH, c(KOH) = 0.05 mol/L



METTLER TOLEDO

Aromatic organic solvents Wastedisposal

Preparation and ProceduresPolyurethane foams, 1-2 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Hydroxyl Value of Polyols

The sample is dissolved in 50 mL ethanol:toluene 1:1 mixture.

Note:A titration in isopropanol gives a more noisy titration curve.

Two titration methods are used:

1) Method BlOH allows the determination of the solvent blankvalue which is automatically stored as auxiliary value H14.

2) Method OH allows the determination of the hydroxide valuein polyols.

Literature:ASTM D2474 (see www.astm.org)

Remarks

Blank determination (Method BlOH):R1 = QR1 is stored as auxiliary value H14

Acid value det. (Method OH):R1 = (Q1 - H14)*C1/mC1 = 56.1

Calculation

Determination of the hydroxyl value of polyols in polyurethane foams ccording to ASTM D2474


Ch. Walter, K. RacmanAuthor

37


METTLER DL77 Titrator V3.1 Mettler-Toledo AG *114* Market Support Laboratory

Method OH Hydr. Value Polyol Ester 31-Jul-1994 13:16UserMeasured 31-Jul-1994 15:48

RESULTS


1/1 1.5022 g Weight m R1 = 1.132 mg KOH/g Hydr. Value 1/2 1.8042 g Weight m R1 = 1.143 mg KOH/g Hydr. Value 1/3 1.7529 g Weight m R1 = 1.155 mg KOH/g Hydr. Value

STATISTICS Number results R1 n = 3 Mean value x = 1.143 mg KOH/gHydr. Value Standard deviation s = 0.011567 mg KOH/gHydr. Value Rel. standard deviation srel = 1.1012 % Outlier test: no outliers!

Titration curve

Results

38

Method OH Hydr. Value Polyol Ester Version 31-Jul-1994 13:16

Title Method ID . . . . . . . . . . . . . OH Title . . . . . . . . . . . . . . . Hydr. Value Polyol Ester Date/time . . . . . . . . . . . . . 31-Jul-1994 13:16Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 6.0 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 100 Time [s] . . . . . . . . . . . . . . 200Titration Titrant . . . . . . . . . . . . . . KOH Concentration [mol/L] . . . . . . . 0.05 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.2 Titrant addition . . . . . . . . INC ∆V [mL] . . . . . . . . . . . 0.025 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 700 Maximum volume [mL] . . . . . . . 2.0 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Hydr. Value Formula . . . . . . . . . . . . . . R1=(Q-H14)*C1/m Constant . . . . . . . . . . . . . . C1=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod BlOH Blank Hydr. Value Polyol Version 31-Jul-1994 12:27

Title Method ID . . . . . . . . . . . . . BlOH Title . . . . . . . . . . . . . . . Blank Hydr. Value Polyol Date/time . . . . . . . . . . . . . 31-Jul-1994 12:27Sample Number samples . . . . . . . . . . . 2 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 100.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . KOH Concentration [mol/L] . . . . . . . 0.05 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . INC ∆V [mL] . . . . . . . . . . . 0.01 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 100 Maximum volume [mL] . . . . . . . 3.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . H14=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes

39

M095

Isocyanate groups, -NCO

25 mL monochlorobenzene10 mL diisobutylamine in Cl-benzene20 mL methylethlyketone

Hydrochloric acid, HCl, in methanolc(HCl) = 1 mol/L


R-NCO + NH(iBu)2 = (iBu)2N-CO-NHR

NH(iBu)2 + HCl = (H2N(iBu)2)+ Cl-

Glass titration beaker ME-101446Printer, balanceComplete automation: additional buretteDV1010, or use a DU200 Dosing unit.

METTLER TOLEDO

Isocyanates solution: special wasteAromatic organic solvents

Wastedisposal

Preparation and ProceduresResin (Desmodur), 4-5 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Determination of Isocyanate Content

1) Dissolve the sample in 25 mL monochlorobenzene and 20mL methylethylketone.

2) Add manually 10 mL 2 mol/L diisobutylamine inchlorobenzene or by means of an additional burette or a DU200Dispensing unit.

3) Start back titration of excess diisobutylamine withhydrochloric acid.

Note:Isocyanates are toxic compounds. Appropriate workingcondictions are needed (fumehood, gloves, googles).

The stirring time must be long enough to ensure completedissolution and reaction of the sample before the back titrationstarts. In most cases, chlorobenzene is able to dissolve thesample. If this is not the case, the mixture can be heated usinga thermostatable beaker with a reflux condenser. The samplesolution should not be overheated since diisobutylamine mightdecompose. If the sample solution becomes turbid, a morediluted solution in a larger titraiton vessel must be used.

Auxiliary solvents (depending on the sample):methylethylketone,methanol, ethanol, acetone

The isocyanate content is an indication for the number ofisocyanate groups -NCO in the sample.The determination is achieved by a back titration. An excessdiisobutylamine is added to the non-aqueous sample solution.Diisobutylamine reacts with isocyanate groups during thestirring time of 300 s. Unreacted diisobutylamine issubsequently titrated with hydrochloric acid.

Two titration methods are used:1) Method 095B allows the determination of the solvent blankvalue which is automatically stored as auxiliary value H15.2) Method 095A allows the determination of the isocyanatecontent.

Hints:1) Rinse accurately the electrode, the stirrer and the burette tipwith e.g. acetone at the end of the titration series.2) The DG113 electrode should be conditioned in pH buffer 7over night to hydrate the pH glass membrane.

Literature:DIN 53185, 16945 (see www.din.de)See also ASTM D1638 (www.astm.org)

Remarks

Blank determination (Method 095B):R1 = QR1 is stored as auxiliary value H15

Acid value det. (Method 095A):R1 = (H15-Q1)*C1/mC1 = M/(10*z)

Calculation

Determination of the isocyanate content in resins according to DIN 53185 and 16945

Standard THAM


40


METTLER DL67 Titrator V3.1 Mettler-Toledo AG DL67(1) Market Support Laboratory

Method 095A Isocyanate:Sample Titr. 17-Aug-1994 16:03UserMeasured 18-Aug-1994 13:53

RESULTS


1/1 NCO 4594 4.0 g Weight m R1 = 9.881 % NCO Isocyanate 1/2 NCO 4594 4.0 g Weight m R1 = 12.874 % NCO Isocyanate 1/3 NCO 4594 4.0 g Weight m R1 = 12.902 % NCO Isocyanate 1/4 NCO 4594 4.0 g Weight m R1 = 12.892 % NCO Isocyanate 1/5 NCO 4594 4.0 g Weight m R1 = 12.880 % NCO Isocyanate 1/6 NCO 4594 4.0 g Weight m R1 = 12.892 % NCO Isocyanate 1/7 NCO 4594 4.0 g Weight m R1 = 12.898 % NCO Isocyanate

STATISTICS Number results R1 n = 7 Mean value x = 12.460 % NCO Isocyanate Standard deviation s = 1.137420 % NCO Isocyanate Rel. standard deviation srel = 9.129 %

Outlier test : sample No. 1/1 Number results R1 n = 6 Mean value x = 12.890 % NCO Isocyanate Standard deviation s = 0.010834 % NCO Isocyanate Rel. standard deviation srel = 0.084 %

Titration curve

Results

41

Method 095A Isocyanate:Sample Titr. Version 17-Aug-1994 16:03

Title Method ID . . . . . . . . . . . . . 095A Title . . . . . . . . . . . . . . . Isocyanate:Sample Titr. Date/time . . . . . . . . . . . . . 17-Aug-1994 16:03Sample Number samples . . . . . . . . . . . 7 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . NCO Molar mass M . . . . . . . . . . . . 42.0171 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . Dibutylamine Concentration [mol/L] . . . . . . . 2.0 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 300Titration Titrant . . . . . . . . . . . . . . HCl (MeOH) Concentration [mol/L] . . . . . . . 1.0 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 100 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . -500 Limit B . . . . . . . . . . . +500 Maximum volume [mL] . . . . . . . 30.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Isocyanate Formula . . . . . . . . . . . . . . R1=(H15-Q)*C1/m Constant . . . . . . . . . . . . . . C1=M/(10*z) Result unit . . . . . . . . . . . . % NCO Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod 095B Isocyanate:Blank Determin. Version 17-Aug-1994 16:03

Title Method ID . . . . . . . . . . . . . 095B Title . . . . . . . . . . . . . . . Isocyanate:Blank Determin. Date/time . . . . . . . . . . . . . 17-Aug-1994 16:03Sample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . Reagent Molar mass M . . . . . . . . . . . . 129.25 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . Dibutylamine Concentration [mol/L] . . . . . . . 2.0 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 300Titration Titrant . . . . . . . . . . . . . . HCl (MeOH) Concentration [mol/L] . . . . . . . 1.0 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 17.5 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 100 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . -500 Limit B . . . . . . . . . . . +500 Maximum volume [mL] . . . . . . . 30.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Isocyan.Blank Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Blank Isocyanate val Formula . . . . . . . . . . . . . . H15=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

42

M235

Isocyanate groups, -NCO

20 mL methylethlyketone10 mL diisobutylamine in isopropanol50 mL isopropanol

Hydrochloric acid, HCl, in isopropanolc(HCl) = 1 mol/L


R-NCO + NH(iBu)2 = (iBu)2N-CO-NHR

NH(iBu)2 + HCl = (H2N(iBu)2)+ Cl-

Glass titration beaker ME-101446Printer, balanceComplete automation: two add. burettesDV1010, or use a DU200 Dosing unit.

METTLER TOLEDO

Isocyanates solution: special wasteAromatic organic solvents

Wastedisposal

Preparation and Proceduresdiphenylmethane-4,4-diisocyanate,0.5 g

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

NCO-Content of Isocyanates by Backtitration

1) Dissolve the sample in 20 mL methylethylketone.

2) Add manually 10 mL 2 mol/L diisobutylamine in isopro-panol or by means of an additional burette or a DU200 unit.

3) Add 50 mL isopropanol by means of an additional burette orby using a peristaltic pump.

4) Start back titration of excess diisobutylamine with HCl.


The stirring time must be long enough to ensure completedissolution and reaction of the sample before the back titrationstarts.

Acidic or basic compounds in the sample interfere.

Instead of diisobutylamine also di-n-butylamine can be used asa reagent. Toluene can also serve as an alternative solvent forthe sample as well as for the titrant.

Use dried solvents and reagents.

The isocyanate content is an indication for the number ofisocyanate groups -NCO in the sample.The determination is achieved by a back titration. An excessdiisobutylamine is added to the non-aqueous sample solution.Diisobutylamine reacts with isocyanate groups during thestirring time of 240 s. Unreacted diisobutylamine issubsequently titrated with hydrochloric acid.

Two titration methods are used:1) Method NCOB allows the determination of the solvent blankvalue which is automatically stored as auxiliary value H16.2) Method NCO allows the determination of the isocyanatecontent.

Hints:1) Rinse accurately the electrode, the stirrer and the burette tipwith e.g. acetone at the end of the titration series.2) The DG113 electrode should be conditioned in pH buffer 7over night to hydrate the pH glass membrane.

Literature:ASTM D1638 (www.astm.org)DL40RC Application No. 163

Remarks

Blank determination (Method NCOB):R1 = QR1 is stored as auxiliary value H16

Acid value det. (Method NCO):R1 = (H16-Q1)*C1/mC1 = M/(10*z)

Calculation

Determination of the isocyanate content in diphenylmethane-4,4-diisocyanate, 0.5 g

Standard THAM


43


DL40RC:

*** 28-JAN-86 ***

INPUT:WEIGHT .5203IDENT. 12.51


*R * % 32.718

STATISTICS:

N 6MEAN 32.823STAND.DEV.% 0.29

Titration curve

Results

44

Method NCO Isocyanate Version 31-Jan-1994 14:30

Title Method ID . . . . . . . . . . . . . NCO Title . . . . . . . . . . . . . . . Isocyanate Date/time . . . . . . . . . . . . . 31-Jan-1994 14:30Sample Number samples . . . . . . . . . . . 5 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.4 Upper limit [g] . . . . . . . . . 0.5 ID1 . . . . . . . . . . . . . . . . NCO Molar mass M . . . . . . . . . . . . 42.0171 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . Dibutylamine Concentration [mol/L] . . . . . . . 2.0 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 300Dispense Titrant . . . . . . . . . . . . . . Isopropanol Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 50.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . HCl (IPA) Concentration [mol/L] . . . . . . . 1.0 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 500 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . -500 Limit B . . . . . . . . . . . +500 Maximum volume [mL] . . . . . . . 25.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Isocyanate Formula . . . . . . . . . . . . . . R1=(H16-Q)*C1/m Constant . . . . . . . . . . . . . . C1=M/(10*z) Result unit . . . . . . . . . . . . % NCO Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod NCOB Isocyanate:Blank Version 31-Jan-1994 14:32

Title Method ID . . . . . . . . . . . . . NCOB Title . . . . . . . . . . . . . . . Isocyanate:Blank Date/time . . . . . . . . . . . . . 31-Jan-1994 14:32Sample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . Reagent Molar mass M . . . . . . . . . . . . 129.25 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . Dibutylamine Concentration [mol/L] . . . . . . . 2.0 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 300Dispense Titrant . . . . . . . . . . . . . . Isopropanol Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 50.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . HCl (MeOH) Concentration [mol/L] . . . . . . . 1.0 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 17.5 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 500 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . -500 Limit B . . . . . . . . . . . +500 Maximum volume [mL] . . . . . . . 30.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Isocyan.Blank Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Blank Isocyanate val Formula . . . . . . . . . . . . . . H16=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

45

M236

Free HCl and isocyanate groups, -NCO

40 mL methanol

Sodium hydroxide, NaOH, in methanolc(NaOH) = 0.1 mol/L


HCl + NaOH = H2O + NaCl

R-NCO + NaOH = ??

Glass titration beaker ME-101446Printer, balance

METTLER TOLEDO

Isocyanates solution: special wasteOrganic solvents

Wastedisposal

Preparation and Proceduresresins, 0.5-1 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Determination of Free HCl and Isocyanates

1) Dissolve the sample in 40 mL methanol.

2) Start titration with sodium hydroxide.


The titrant must be protected from CO2-intake from the air.

Hints:1) The DG113 electrode should be conditioned in pH buffer 7over night to hydrate the pH glass membrane.

2) Clean the electrode and the stirrer after each sample titrationwith eg. methanol.

Remarks

Free HCl content:R1 = Q1*C1/m ; %C1 = 36.5/(10*z)

Isocyanate content:R2 = Q2*C2/m ; %C2 = M/(10*z)

Calculation

Determination of the content of free hydrochloric acid and isocyanate by titration with sodium hydroxide in amethanolic sample solution.

Standard KHP

Roland Boehlen, MT-CHAuthor

46


METTLER DL70 Titrator

7 Free HCl and Isocyanate measured 26-Oct-1992 12:3826-Oct-1992 12:09 TitratorSW Version 2.0 User BR****

SAMPLE Nr. 1/1 Titration stand Stand 1 Identification R-N:C:O Weight m = 0.5654 g Correction factor f = 1.0

TITRATION Titrant NaOH 0.1 mol/L t = 1.0 Concentration Drive 2 20 mL Sensor DG113-SC

Consumption EQP 1 VEQ1 = 0.42703 mL Q1 = 0.04270 mmol EPOT1 = 423.4 mV Consumption EQP 2 VEQ2 = 6.25668 mL Q2 = 0.62567 mmol EPOT2 = -318.8 mV Excess VEX = 0.02829 mL QEX = 0.00283 mmol

CALCULATION Result R1 = 0.28 % Free HCl

CALCULATION Result R2 = 28.94 % R-N:C:O

Titration curve

Results

47

Method 7 Free HCl and Isocyanate Version 26-Oct-1992 12:09

Title Method ID . . . . . . . . . . . . . 7 Title . . . . . . . . . . . . . . . Free HCl and Isocyanate Date/time . . . . . . . . . . . . . 26-Oct-1992 12:09Sample Number samples . . . . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.4 Upper limit [g] . . . . . . . . . 0.6 ID1 . . . . . . . . . . . . . . . . R-N:C:O Molar mass M . . . . . . . . . . . . 261.5 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 100Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 1.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 500 Maximum volume [mL] . . . . . . . 25.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 2 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Free HCl Formula . . . . . . . . . . . . . . R1=Q1*C1/m Constant . . . . . . . . . . . . . . C1=36.5/(10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 2Calculation Result name . . . . . . . . . . . . R-N:C:O Formula . . . . . . . . . . . . . . R2=Q2*C2/m Constant . . . . . . . . . . . . . . C2=M/(10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 2Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Method

48

M096

Carbon-carbon double bons, -CH=CH-

10 mL Glacial acetic acid:Cyclohexane 1:415 mL, Wijs-sol.: with ICl, c(ICl) = 0.1 M5 mL , Potassium iodide, KI, c(KI) = 1 mol/L20 mL, deionized water

Sodium thiosulfate, Na2S2O3

c(Na2S2O3)=0.1 mol/L

DL70ES, DL77

I2 + -CH=CH- = -CHI-IHC-

I2 + 2S2O32- = S4O6

2- + 2I-

Glass titration beaker ME-101446Rondo 60 with two diaphragm pumps,Printer, balancetwo additional burettes DV1020

METTLER TOLEDO

Organic solvents Wastedisposal

Preparation and ProceduresResins and oils, 0.2-0.7 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM140-SCIndication

Iodine Value in Resins and Oils According to Wijs

1) The sample is dissolved in 10 mL solvent mixture consistingof glacial acetic acid:cyclohexane 1:4 .

2) 15 mL Wijs solution are added automatically by a DV1020burette. The reaction is stirred during 60 s, and the electrodeand stirrer are rinsed with 10 mL ethanol with the diaphragmpump. Use flexible conditioning setup with yellow cllips.

3) The function "Conditioning" is used to allow the samplesolution to react completely during 1000 s. If the time is notenough, then the reaction time can be increased by repeatinmgthe function "Conditioning" (loop).

4) 5 mL potassium iodide are added by a second burette, andthe second diaphragm pump adds 20 mL deionized water.

5) Excess iodine is back-titrated using sodium iodine. Theelectrode is rinsed with 10 mL ethanol.

Iodine value:The iodine value in the amount of ioding in g which reacts withthe carbon double bonds in 100 g of sample (unsaturatedbonds). It indicates the degree of unsaturation of the sample.

Two titration methods are used:1) Method 096B allows the determination of the solvent blankvalue which is automatically stored as auxiliary value H17.2) Method 096A allows the determination of the iodine value byback titration of excess iodine with sodium thiosulphate.

Hints:1) The sample must be completely dissolved before addition ofWijs redution. The stirring time must be selected accordingly. Ifnecessary, a ultrasonic bath can be used to dissolve sample.2) The composition of the solvent mixture must be adapted tothe sample. In this case, the most appropriate solvent is amixture fo glacial acetic acid and cyclohexane.3) The appropriate stirring speed for the back titration must bechosen to get an homogeneous phase system.

Literature:DIN 53241 (www.din.de)Application M051

Remarks


Iodine value det. (Method 096A):R1 = (H17-Q1)*C1/mC1 = M/(10*z)

Calculation

Determination of the iodine value in resins and oils according to DIN 53241

Standard Potassium iodate, KIO3 (see M526)


49



1/1 Dammar Resin 25.0 mL Fixed volume U R1 = 1 LOOP .......................................................... 1/5 Dammar Resin 25.0 mL Fixed volume U R1 = 1 LOOP 1/6 Dammar Resin 25.0 mL Fixed volume U R1 = 1 LOOP 1/7 Dammar Resin 25.0 mL Fixed volume U R1 = 1 LOOP 2/1 Dammar Resin 0.275 g Weight m R2 = 79.81 g I2/100g Iodine number 2/2 Dammar Resin 0.275 g Weight m R2 = 74.10 g I2/100g Iodine number 2/3 Dammar Resin 0.275 g Weight m R2 = 73.39 g I2/100g Iodine number 2/4 Dammar Resin 0.275 g Weight m R2 = 72.53 g I2/100g Iodine number 2/5 Dammar Resin 0.275 g Weight m R2 = 72.07 g I2/100g Iodine number 2/6 Dammar Resin 0.275 g Weight m R2 = 71.91 g I2/100g Iodine number 2/7 Dammar Resin 0.275 g Weight m R2 = 71.69 g I2/100g Iodine numberSTATISTICS Number results R1 n = 7 Mean value x = 1 LOOPSTATISTICS Number results R2 n = 7 Mean value x = 73.64 g I2/100g Iodine number Standard deviation s = 2.852742 g I2/100g Iodine number Rel. standard deviation srel = 3.874 % Outlier test : sample No. 2/1 Number results R1 n = 6 Mean value x = 72.62 g I2/100g Iodine number Standard deviation s = 0.942869 g I2/100g Iodine number Rel. standard deviation srel = 1.298 %

Weitere Resultate:Sample Mass (g) n x (g/100g) srel (%) Time (min)

Kolophonium 0.41 7 60.59 0.66 4Dammharz 0.275 6 72.62 1.30 6Lärchenöl 0.2326 7 101.62 0.85 4Leinöl 0.1008 4 176.10 0.56 5

Blank value H17 5 2.9417 mmol 0.04 4

Titration curve

Results

50

Method 096A Wijs Iodine Number Version 10-May-1994 9:45

Title Method ID . . . . . . . . . . . . . 096A Title . . . . . . . . . . . . . . . Wijs Iodine Value Date/time . . . . . . . . . . . . . 10-May-1994 9:45Sample Number samples . . . . . . . . . . . 7 Titration stand . . . . . . . . . . ST20 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . Polymer Molar mass M . . . . . . . . . . . . 254 Equivalent number z . . . . . . . . 2 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . Wijs solution Concentration [mol/L] . . . . . . . 0.1 Volume [mL] . . . . . . . . . . . . 15.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 60Calculation Result name . . . . . . . . . . . . LOOP Formula . . . . . . . . . . . . . . R1=1 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0Rinse Auxiliary reagent . . . . . . . . . Ethanol Volume [mL] . . . . . . . . . . . . 10.0Statistics Ri (i=index) . . . . . . . . . . . . R1Dispense Titrant . . . . . . . . . . . . . . Isopropanol Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 50.0Stir Speed [%] . . . . . . . . . . . . . 0 Time [s] . . . . . . . . . . . . . . 0Conditioning Interval . . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . . 1000Sample Number samples . . . . . . . . . . . 7 Titration stand . . . . . . . . . . ST20 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . Polymer Molar mass M . . . . . . . . . . . . 254 Equivalent number z . . . . . . . . 2 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . KI (1) Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 5.0Pump Auxiliary reagent . . . . . . . . . H2O Volume [mL] . . . . . . . . . . . . 20.0Stir Speed [%] . . . . . . . . . . . . . 70 Time [s] . . . . . . . . . . . . . . 60

MethodTitration Titrant . . . . . . . . . . . . . . Na2S2O3

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.4 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 6.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 300 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . 1000 Limit B . . . . . . . . . . . -1000 Maximum volume [mL] . . . . . . . 50.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Iodine Number Formula . . . . . . . . . . . . . . R1=(H17-Q)*C1/m Constant . . . . . . . . . . . . . . C1=M/(10*z) Result unit . . . . . . . . . . . . % NCO Decimal places . . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . VEQ>0Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . VEQ>0Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . VEQ<=0Rinse Auxiliary reagent . . . . . . . . . Ethanol Volume [mL] . . . . . . . . . . . . 10.0Statistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . YesConditioning Interval . . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . . 60 Rinse . . . . . . . . . . . . . . . Yes Auxiliary reagent . . . . . . . . H2O Volume [mL] . . . . . . . . . . . 10.0

Blank Determination:Method 096B is used for the blank determination and is similarto method 096A. The blank value is stored as auxiliary valueH17 (function "Auxiliary value")

51

M051

C-C double bonds, -CH=CH-

15 mL carbon tetrachloride, CCl4 ;25 mL Wijs solution; 100mL water;15 mL 10% potassium iodide, KI

Sodium thiosulphate, Na2S2O3

c(Na2S2O3)=0.1 mol/L;

DL70, AT250, Matrix printer EPSONFX800 with serial interface

ICl3 + I2 = 3 ICl

ICl + KI = I2 + KCl

2(SO3S)2- + I2 = 2 I- + (S2O6S2)2-

250 mL Titration beakers ME-23829,Additional burette drive DV90

METTLER TOLEDO

Halogenated organic solventWastedisposal

Preparation and ProceduresFats and oils, approx. 25 g / expectedIodine value

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM140-SC at Sensor 2Indication

Iodine Value of Edible Oils and Fats According to Wijs (AOAC Method

1) Dissolve the sample in CCl4, add 25 mL Wijs solution andkeep in the dark for approx. 1 hour to complete the reaction.

2) Add deionized water and titrate excess iodine with sodiumthiosulphate.

Wijs solution:Dissolve 16.2 g iodine monochloride (ICl) in a 1 L volumetricflask with glacial acetic acid. Store the Wijs solution in amberbottle sealed with paraffin until it is used.

Wijs solution is sensitive to temperature, moisture and light.Slight variations of the temperature considerably affect titer of theWijs solution. Therefore it is essential that blanks and samplesare titrated at same time.

The mean value of the blank determination (method 051b) isautomatically stored as auxiliary value H3.Typical results:Blank = 4.94 mmol, srel = 0.04%, n = 5

The iodine value is defined as the weight of iodine absorbed by100 g of an oil or fat.

1) The excess of Wijs solution should be 50-60% of theamount added, ie. 100-150% of amount reacted with thesample.

2) If the result will be assumed (e.g. in routinr quality control)the predispensing can be adjusted accordingly in volume orchanged to % nominal content . This also shortens the titrationtime.

3) The addition of 10 mL 2.5% mercury (II) acetate in glacialacetic acid (after Wijs solution is added) shortens the reactiontime to 5 minutes

Literature:AOAC Official Method of Analysis, 1984, Chapter 28.023

Remarks


Iodine value det. (Method 096A):R1 = (H3-Q1)*C1/mC1 = M/(10*z)

Calculation

Method for the determination of iodine value (g I2/100g) of edible oils and fats according to Wijs asindicated by AOAC Official Methods of Analysis (1984), Chapter 28.023

Standard Potassium iodate, KIO3

Ruth von RotzAuthor

52


METTLER DL70 Titrator

051a I2-value of oils and fats

Measured 25-June-1991 3:37 pmUser rvrTitrator PT 2Version SW 2.0

RESULTS No ID1 Weight Results

1/1 cocofat 2.0267 g 11.85 g I2/100 gI2-value





STATISTICS Number results R1 n = 5 Mean value x = 11.85 g I2/100 gI2-value Standard deviation s = 0.013 g I2/100 gI2-value Rel. standard deviation srel = 0.107 %

Various Samples

Sample Weight n Iodine value RSD t (g) (gI2/100g) (%) (min)

Coconut fat 2.00-2.10 5 11.8 0.11 5

Margarine"light" 0.40-0.45 3 37.3 0.26 5

Lard 0.40-0.45 5 57.6 0.13 5

Olive oil 0.20-0.25 5 82.5 0.16 6

Margarine 0.50-0.55 3 86.1 0.21 3

Rape oil 0.20-0.25 4 113.4 0.15 5

Sunflower oil 0.20-0.25 3 132.7 0.06 4

Titration curve

Results

53

Method 051a I2 - value of oils and fats Version 19-June-1991 16:21

Title Method ID . . . . . . . . . . . . . 051a Title . . . . . . . . . . . . . . . I2 - value of oils andfats Date/time . . . . . . . . . . . . . 19-June-1991 16:21Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 1.5 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 254 Equivalent number z . . . . . . . . 2Dispense Titrant . . . . . . . . . . . . . . KI 10% Concentration [mol/L] . . . . . . . 10.0 Volume [mL] . . . . . . . . . . . . 15.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 45Titration Titrant . . . . . . . . . . . . . . Na2S2O3H2O Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . 20.0 Predispensing 2 . . . . . . . . . To slope slope [mV,pH, .../mL] . . . . 4.0 Titrant addition . . . . . . . . DYN dE (set)[mV] . . . . . . . . . 0.02 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . 1.0 t (min) [s] . . . . . . . . 6.0 t (max) [s] . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 50.0 Maximum volume [mL] . . . . . . . 50.0 Termination after n EQPs . . . . Yes n = . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . I2 - value Formula . . . . . . . . . . . . . . R=(H3-Q)*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Result unit . . . . . . . . . . . . g I2/100g Decimal places . . . . . . . . . . . 2Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes E - V curve . . . . . . . . . . . . Yes Table of measured values . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

MethodMethod 051b Blank I2 - value Version 19-June-1991 16:15

Title Method ID . . . . . . . . . . . . . 051b Title . . . . . . . . . . . . . . . Blank I2 - value Date/time . . . . . . . . . . . . . 19-June-1991 16:15Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . 25.0 ID1 . . . . . . . . . . . . . . . . Blank Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1Dispense Titrant . . . . . . . . . . . . . . KI 10% Concentration [mol/L] . . . . . . . 10.0 Volume [mL] . . . . . . . . . . . . 15.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 45Titration Titrant . . . . . . . . . . . . . . Na2S2O3H2O Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . 40.0 Predispensing 2 . . . . . . . . . To slope slope [mV,pH, .../mL] . . . . 4.0 Titrant addition . . . . . . . . DYN dE (set)[mV] . . . . . . . . . 4.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . 1.0 t (min) [s] . . . . . . . . 6.0 t (max) [s] . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 50.0 Maximum volume [mL] . . . . . . . 60.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank I2 - value Formula . . . . . . . . . . . . . . R1=Q[1] Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 4Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes E - V curve . . . . . . . . . . . . Yes Table of measured values . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Blank I2 - value Formula . . . . . . . . . . . . . . H3=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

54

M211

C-C double bonds, -CH=CH-

10 mL CCl4 ; 10 mL Wijs solution;20 mL 2.5 % mercury (II) acetate;20 mL 20% potassium iodide, KI

Sodium thiosulphate,c(Na2S2O3)=0.1 mol/L;

DL70, ST20A Sample changer, AT250Balance, Matrix printer EPSON FX800with serial interface

ICl3 + I2 = 3 ICl

ICl + KI = I2 + KCl

2(SO3S)2- + I2 = 2 I- + (S2O6S2)2-

Titration beaker ME-101974,3 Peristaltic pumps ME-65241,1 Additional burette drive DV90

METTLER TOLEDO

Halogenated organic solventscontaining mercury ions.

Wastedisposal

Preparation and ProceduresCosmetic fats, 0.1 - 5 gaccording to the expected iodine value

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM140-SC at Sensor 2Indication

Iodine Value of Cosmetic Fats According to Wijs

1) Dissolve the sample in 10 mL carbon tetrachloride. The Wijssolution, mercuric acetate and potassium iodide solution areadded automatically by the DL70 titrator.

2) The mercuric acetate in glacial acetic acid, which is onlyadded after the Wijs reagent, is used to speed up the reaction.

3) It is important to determine the blank 3 times before theiodine value determination. The mean value of the three blankdeterminations is stored as auxiliary value (H3).

Note:1. Wijs solution, c(ICl) = 0.2 mol/L

2. The 2.5% solution is prepared by dissolving mercury (II)acteta in glacial acetic acid.

The iodine value is defined as the amount of iodine which reactswith 100 g of an oil or fat.

Literature:See Application No. M051, M096 and M617

Remarks

Blank value:R1 = Q1[1] ; in mmolR1 is stored as auxiliary value H3

Iodine value:R2 = (H3-Q1[2])/m ; mmol/g

Calculation

Method for the determination of the iodine value of cosmetic fats according to Wijs.


Angelo BonettiAuthor

55


METTLER DL70 Laboratorio controllo M.P.

Automatic: Indice di Iodio

Measured 01-Dec-1989 11:23User RGFTitration 01-Dec-1989 09:46Version SW 1.2

RESULTS

No ID1 Volume Results

1/1 Bianco J 10.0 mL 1.7659 mmol Bianco J

1/2 Bianco J 10.0 mL 1.7682 mmol Bianco J

1/3 Bianco J 10.0 ml 1.7688 mmol Bianco J

2/1 No. Iodio 0.151 g 87.74 gI 2/100g Indice Iodio



STATISTICS Number results n = 3 Mean value x = 1.7676 mmol Bianco J Standard deviation s = 0.00152 mmol Bianco J Rel. standard deviation srel = 0.086 %

STATISTICS Number results n = 3 Mean value x = 87.80 gI 2/100g Indice Iodio Standard deviation s = 0.056 gI 2/100g Indice Iodio Rel. standard deviation srel = 0.064 %

AUXILIARY VALUE Nouvelle value H3 = 1.767644 Bianco del Wijs

Titration curve

Results

56

Method 211 Automatiz. Indice di Iodio Version 30-Nov-1989 11.27

Title Method ID . . . . . . . . . . . . . 211 Title . . . . . . . . . . . . . . . Automatiz.Indice diIodio Date/time . . . . . . . . . . . . . 30-Nov-1989 11.27Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . Bianco J Molar mass M . . . . . . . . . . . . 1.0 Equivalent number z . . . . . . . . 1Dispense Titrant . . . . . . . . . . . . . . Reatt.di Wijs Concentration . . . . . . . . . . . 0.2 Volume [mL] . . . . . . . . . . . . 10.0Dispense Titrant . . . . . . . . . . . . . . (CH3COO)2Hg Concentration . . . . . . . . . . . 0.0 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 120Auxilliary instrument Name . . . . . . . . . . . . . . . . Pompa KI Time [s] . . . . . . . . . . . . . . 3.0Stir Speed [%] . . . . . . . . . . . . . 100 Time [s] . . . . . . . . . . . . . . 30Titration Titrant . . . . . . . . . . . . . . Na2S2O3 Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM-140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predespensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 16.0 Predespensing 2 . . . . . . . . . f (potential) Potential (mV,pH...) . . . . . 230.0 Titrant addition . . . . . . . . INC dV [mL] . . . . . . . . . . 0.05 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 10.0 Threshold . . . . . . . . . . . . 350.0 Maximum volume [mL] . . . . . . . 25.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . AsymmetricRinse Solution aux. . . . . . . . . . . . H2O Volume [mL] . . . . . . . . . . . . 10.0Calculation Result name . . . . . . . . . . . . Bianco J Formula . . . . . . . . . . . . . . R1=Q1[1] Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 4Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Bianco del Wijs Formula . . . . . . . . . . . . . . H3=xRecord All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . YesSample Number samples . . . . . . . . . . . 1 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Poids m Lower limit [g] . . . . . . . . . 0.05 Upper limit [g] . . . . . . . . . 2.0 ID1 . . . . . . . . . . . . . . . . No. Iodio Molar mass M . . . . . . . . . . . . 254 Equivalent number z . . . . . . . . 2

MethodDispense Titrant . . . . . . . . . . . . . . Reatt.di Wijs Concentration . . . . . . . . . . . 0.2 Volume [mL] . . . . . . . . . . . . 10.0Dispense Titrant . . . . . . . . . . . . . . (CH3COO)2Hg Concentration . . . . . . . . . . . 0.0 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 65 Time [s] . . . . . . . . . . . . . . 300Auxilliary instrument Name . . . . . . . . . . . . . . . . Pompa KI Time (s) . . . . . . . . . . . . . . 3.0Stir Speed [%] . . . . . . . . . . . . . 100 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . Na2S2O3 Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM-140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predespensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 16.0 Titrant addition . . . . . . . . DYN dV (set) [mL] . . . . . . . . 5.0 Limits dV . . . . . . . . . . Absolute dV (min) [mL] . . . . . . . . 0.03 dV (max) [mL] . . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 10.0 Threshold . . . . . . . . . . . . 200.0 Maximum volume [mL] . . . . . . . 25.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . AsymmetricRinse Solution aux. . . . . . . . . . . . H2O Volume [mL] . . . . . . . . . . . . 10.0Calculation Result name . . . . . . . . . . . . Indice Iodio Formula . . . . . . . . . . . . . . R2=(H3-Q[2])*C2/m Constant . . . . . . . . . . . . . . C2=M/(10*z) Result unit . . . . . . . . . . . . gI2/100g Decimal places . . . . . . . . . . . 2Statistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes

57

M206

Carboxyl goups, -COOH

50 mL solvent mixture(Chloroform:phenol 3:2)Indic.: bromphenol blue in ethanol

Potassium hydroxide in benzyl alcohol,c(KOH)=0.02 mol/L

DL70/DL77Balance, printer

Titration beaker ME-101974Adapter cable DIN-Lemo ME-89600

METTLER TOLEDO

Halogenated organic solventsWastedisposal

Preparation and ProceduresAmorphous PET, 1 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DP550 Phototrode, colour indicator:0.1% Bromphenol blue in ethanol

Indication

Determination of Carboxyl Groups in PET

1) The sample is heated in 50 mL solvent mixture(chloroform:phenol, 3:2) during 1 hour at 130°C using a refluxcondenser.

2) After cooling down at room temperature, the sample istitratedwith potassium hydroxide and bromphenol blue as an indicator.

3) A DP550 phototrode is used to monitor the colour chang eofthe indicator from yello to blue.

4) A blank value is determined previous tiraiton of the sample.The blank value is stored as auxiliary value H18.

1) The titer determination is performed using potassiumhydrogen phtalate, KHP, as a primary standard:KHP is dissolved in 10 mL deionized water and diluted to 100mL with benzyl alcohol. 2 mL of this solution was added to 50mL benzyl alcohol and titrated with KOH.Phenolphtalein in ethanol is used as colour indicator.

2) The DP550 phototrode has to be adjusted to approximately1000 mV by dipping it in deionized water and turning the knobon the top of the housing.

3) The sensor and the stirrer have to be cleaned thoroughly withwater and benzyl alcohol afte reach sample deteremination.

Literature:See Application No. M051, M096 and M617

Remarks

R=Q*C/mC=1000 , in eq/ton

Calculation

Carboxyl groups, -COOH, in PET are determined by non-aqueous titration with KOH

Standard KHP in benzyl alcohol

Viola SchindlerAuthor

58


METTLER DL77 Titrator V3.1 Mettler - Toledo AG 23 Market Support Laboratory

Method 206A COOH in PET determination 08-Jan-1997 12:44User V. SchindlerMeasured 08-Jan-1997 17:44

RESULTS


1/1 COOH 1.0008 g Weight m R1 = 21.39511 eq/ton COOH content R2 = 1.3474 mL mL consump 1/2 COOH 1.0008 g Weight m R1 = 21.51753 eq/ton COOH content R2 = 1.3551 mL mL consump 1/3 COOH 1.0008 g Weight m R1 = 21.14597 eq/ton COOH content R2 = 1.3317 mL mL consump

STATISTICS Number results n = 3 Mean value x = 21.35287 eq/ton COOH content Standard deviation s = 0.189344 eq/ton COOH content Rel. standard deviation srel = 0.887 % Outlier test: no outliers!

Titration curve

Results

59

Method 206A COOH in PET determination Version 08-Jan-1994 12:44

Title Method ID . . . . . . . . . . . . . 206A Title . . . . . . . . . . . . . . . COOH in PET determination Date/time . . . . . . . . . . . . . 08-Jan-1994 12:44Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 7.0 ID1 . . . . . . . . . . . . . . . . COOH Molar mass M . . . . . . . . . . . . 54.02 Equivalent number z . . . . . . . . 1 Temeprature sensor . . . . . . . . . ManualInstruction Add bromphenol BlueStir Speed [%] . . . . . . . . . . . . . 80 Time [s] . . . . . . . . . . . . . . 40Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 2Titration Titrant . . . . . . . . . . . . . . KOH Concentration [mol/L] . . . . . . . 0.02 Sensor . . . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . INC dV [mL] . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . 40.0 Threshold . . . . . . . . . . . . 250.0 Maximum volume [mL] . . . . . . . 3.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . COOH content Formula . . . . . . . . . . . . . . R=(Q-H18)*C/m Constant . . . . . . . . . . . . . . C=1000 Result unit . . . . . . . . . . . . eq/ton Decimal places . . . . . . . . . . . 5Calculation Result name . . . . . . . . . . . . mL consump Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mL Decimal places . . . . . . . . . . . 4Record Output unit . . . . . . . . . . . . Printer Sample data . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes

MethodMethod 206B Blank: COOH in PET Version 08-Jan-1994 12:47

Title Method ID . . . . . . . . . . . . . 206B Title . . . . . . . . . . . . . . . Blank: COOH in PET Date/time . . . . . . . . . . . . . 08-Jan-1994 12:47Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . COOH Molar mass M . . . . . . . . . . . . 54.02 Equivalent number z . . . . . . . . 1 Temeprature sensor . . . . . . . . . ManualInstruction Add bromphenol BlueStir Speed [%] . . . . . . . . . . . . . 80 Time [s] . . . . . . . . . . . . . . 40Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 2Titration Titrant . . . . . . . . . . . . . . KOH Concentration [mol/L] . . . . . . . 0.02 Sensor . . . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . INC dV [mL] . . . . . . . . . . 0.02 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . 40.0 Threshold . . . . . . . . . . . . 250.0 Maximum volume [mL] . . . . . . . 3.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 5Record Output unit . . . . . . . . . . . . Printer Sample data . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . H18=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

60

M237

Peroxide, ROOR

12 mL Chloroform, CHCl3 , 18 mLglacial acetic acid, 0.5 mL saturatedKI solution, 30 mL deion. water, starch


c(Na2S2O3)= 0.01mol/L;

DL50 Graphix

2R-OOH + 2KI = 2R-OH + 2KOH + I2

I2 + 2Na2S2O3 = 2NaI + Na2S4O6


METTLER TOLEDO

Halogenated organic solventsWastedisposal

Preparation and ProceduresLecithin, 5 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM140-SCIndication

Peroxide Value of Lecithin

1) Lecithin is dissolved in a solvent mixture consisting of 12 mLchloroform and 18 mL glacial acetic acid.

2) After manually adding 0.5 mL saturated potassium iodidesolution, the sample is stirred 60 s using the auxiliary functionStir of the titrator. Iodine is generated.

3) 30 mL deionised water are added to the sample together withstarch.

4) The sample is titrated using sodium thiosulphate.

Note:Starch is added in order to select the most appropriate titarntincrement size for the titration depending on the colour obtained:

Faint blue: increment size 0.05 mLDark blue: increment size 0.5 mL

A blank value is determined previous sample titration.

This application was perforemd with theDL40RC titrator and themethod was adapted tot he DL50 Graphix.The method can be completely automated using a DL58 or aDL7x titrator using the flexible method concept.


Remarks

Peroxide value det. (Method 40014)R = (Q-H2)*C/mC=1000 , meq O2/kg

Blank determination (Method 40015)R = Q ; mmolR is stored as auxiliary value H2

Calculation

Determination of the peroxide value of lecithin


R. Günter, MT-DAuthor

61


DL40RC:

*** 20-NOV-81 ***


*R * .10000

STATISTICS:

N 5MEAN 3.5STAND.DEV.% 3.1

Titration curve

Results

62

Method 40014 Peroxide value Version 7-Feb-2002 11:00

Title Method ID . . . . . . . . . . . . . 40014 Title . . . . . . . . . . . . . . . Peroxide value Date/time . . . . . . . . . . . . . 7-Feb-2002 11:00Sample Sample ID . . . . . . . . . . . . . Lecithin Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 4.0 Upper limit [g] . . . . . . . . . 6.0 Molar mass M . . . . . . . . . . . . 1.0 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10EQP Titration Titrant . . . . . . . . . . . . . . Na2S2O3 Concentration [mol/L] . . . . . . . 0.01 Sensor . . . . . . . . . . . . . . . DM140 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Incremental dV[mL] . . . . . . . . . . . . . 0.05 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.2 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 200 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 30.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=(Q-H1)*C1/m Constant . . . . . . . . . . . . . . C1=1000 Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . meq O2/kg Result name . . . . . . . . . . . . Peroxide value Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 5 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Report Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

MethodMethod 40015 Blank Version 7-Feb-2002 11:05

Title Method ID . . . . . . . . . . . . . 40015 Title . . . . . . . . . . . . . . . Blank Date/time . . . . . . . . . . . . . 11-Dec-2001 11:05Sample Sample ID . . . . . . . . . . . . . Blank peroxide Entry type . . . . . . . . . . . . . Volume Volume [mL] . . . . . . . . . . . 60.05 Molar mass M . . . . . . . . . . . . 1.0 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10EQP Titration Titrant . . . . . . . . . . . . . . Na2S2O3 Concentration [mol/L] . . . . . . . 0.01 Sensor . . . . . . . . . . . . . . . DM140 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Incremental dV[mL] . . . . . . . . . . . . . 0.02 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.2 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 200 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 5.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 5 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Auxiliary value ID text . . . . . . . . . . . . . . Blank peroxide Formula . . . . . . . . . . . . . . H2=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

63

M624

Peroxide, ROOR

20 mL acetic acid/chloroform1 mL saturated KI solution50 mL deion. water


c(Na2S2O3)= 0.01mol/L;

DL58; DL70ES/DL77

2R-OOH + 2KI = 2R-OH + 2KOH + I2

I2 + 2Na2S2O3 = 2NaI + Na2S4O6

Titration beakers ME-101974Balance, Printer

METTLER TOLEDO

The waste contains organic solventsand is disposed accordingly.

Wastedisposal

Preparation and ProceduresOil, fat, margarine ; 3 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM140-SCIndication

Peroxide Value of Edible oils and Fats

1) Beakers have to be cleaned very well. Invisible fat residues ormetal traces can affect the result strongly.

2) About 3 g of sample were dissolved in 20 mL of aceticacid/chloroform (3:2) The acetic acid/chloroform mixture wasadded by the function DISPENSE.

3) 1 mL of saturated potassium iodide solution is addedmanually. Thereaction takes place and iodine is formed.

4) 50 mL deionized water are added manually to the samplesolution. Iodine is titrated with sodium thiosulphate.

Saturated KI solution:127 g KI were dissolved in 100 mL water to obtain thesaturated KI solution. The solution has to be kept in the dark.

Optimum stir timeSeveral measurements were made to evaluate the optimal stirtime. 300 s were found to be the optimum stir time. A stir timeof less than 300 s was found to be insufficient resulting in lowresults.A stir time of more than 300 s leads to secondary reactionsbetween the liberated iodine and the oil.

Blank value determinationImpurities of the solvent are taken into account by a blank valuedetermination. The blank value determination is done under thesame conditions as the peroxide value determination itself. Theblank value is automatically stored as auxiliary value H1 with thefunction AUXILIARY VALUE (see method 91015)

DefinitionsFats and oils undergo changes during storage due to oxidationwith air (oxidative rancidity). The compounds formed react asperoxides. Their content is commonly expressed as the "peroxidevalue" in milliequivalents peroxidic oxygen per kg of sample.Peroxide values higher than 10 to 20 meq O2/kg are commonlyinterpreted as rancidity. Unrefined oils have higher peroxidevalues. They are usually in the range between 5 to 20 meqO2/kg.

Influence stir time

Stir time [s] Result [meq/kg] 60 3.201180 4.947300 6.817600 6.491

Remarks

Peroxide value det. (Method 91016)R = (Q-H1)*C/mC=1000 , meq O2/kg

Blank determination (Method 91015)R=QQ is stored as auxiliary value H1

Calculation

Method for the determination of the peroxide value in oil, fat and margarine.


K. Wydler Author

64


Peroxide value of olive oil

ALL RESULTS

No. ID Sample size and results

1 ROOR 3.2691 g R1 = 16.104 meq/kg Peroxide Val. 2 ROOR 3.1461 g R1 = 16.660 meq/kg Peroxide Val. 3 ROOR 3.1838 g R1 = 16.783 meq/kg Peroxide Val. 4 ROOR 3.2309 g R1 = 16.660 meq/kg Peroxide Val. 5 ROOR 3.0293 g R1 = 16.517 meq/kg Peroxide Val.

Etc.

STATISTICS Number of results R1 n = 5 Mean value x = 16.545 meq/kg Peroxide Val. Standard deviation s = 0.26372 meq/Kg Peroxide Val. Rel. standard deviation srel = 1.594 %

Peroxide value: comparison of different oils and fats

Oil Sample mass n Mean value Stand. Deviation srel [g] [% water] [% water] [%]

Thistle oil 3.0435 - 4.2328 5 18.310 0.35621 1.945Sunflower oil 2.3521 - 4.5656 5 13.880 0.75799 5.461Peanut oil 1.9836 - 3.0248 5 13.179 0.58047 4.405Olive oil 3.0293 - 3.2691 5 16.545 0.26372 1.594Palm oil 2.3217 - 3.8720 5 11.680 0.62599 5.359Margarine 3.9440 - 2.7137 5 8.312 0.45597 5.486Coconut fat 2.0889 - 2.6050 5 5.542 0.23404 4.224

Titration curve

Results

65

Method 91016 Peroxide Value Version 30-Jul-1999 13:14

Title Method ID . . . . . . . . . . . 91016 Title . . . . . . . . . . . . . Peroxide Value Date/time . . . . . . . . . . . 30-Jul-1999 13:14Sample Sample ID . . . . . . . . . . . O2 Entry type . . . . . . . . . . . Weight Lower limit [g] . . . . . . . 0.0 Upper limit [g] . . . . . . . 5.0 Molar mass M . . . . . . . . . . 32.0 Equivalent number z . . . . . . 1 Titration stand . . . . . . . . Stand 1 Temperature sensor . . . . . . . ManualDispense Titrant . . . . . . . . . . . . Chloroform/AA Concentration [mol/L] . . . . . 0.1 Volume [mL] . . . . . . . . . . 20Instruction Text . . . . . . . . . . . . . . Add 1 mL KI solutionStir Speed [%] . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . 300Instruction Text . . . . . . . . . . . . . . Add 50 mL destilled waterEQP titration Titrant/Sensor Titrant . . . . . . . . . . . Na2S2O3 Concentration [mol/L] . . . . 0.01 Sensor . . . . . . . . . . . DM140 Unit of meas . . . . . . . . mV Predispensing . . . . . . . . . No Titrant addition . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . 0.2 Measure mode . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . 200.0 Steepest jump only . . . . . No Range . . . . . . . . . . . . No Tendency . . . . . . . . . . Negative Termination at maximum volume [mL] . . . 20.0 at potential . . . . . . . . No at slope . . . . . . . . . . No afternumber EQPs . . . . . . Yes n = . . . . . . . . . . . 1 comb. term. conditions . . . No Evaluation Procedure . . . . . . . . . . Standard Potential 1 . . . . . . . . . No Potential 2 . . . . . . . . . No Stop for reevaluation . . . . NoCalculation Formula . . . . . . . . . . . . R=(Q-H1)*C/m Constant . . . . . . . . . . . . C=1000 Decimal places . . . . . . . . . 3 Result unit . . . . . . . . . . meq/kg Result name . . . . . . . . . . Peroxide Val. Statistics . . . . . . . . . . . YesReport Output . . . . . . . . . . . . Printer Results . . . . . . . . . . . . No All results . . . . . . . . . . Yes Raw results . . . . . . . . . . Yes Table of measured values . . . . Yes Sample data . . . . . . . . . . Yes E - V curve . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . Yes

MethodMethod 91015 Blank Peroxide Value Version 30-Jul-1999 12:18

Title Method ID . . . . . . . . . . . 91015 Title . . . . . . . . . . . . . Blank Peroxide Value Date/time . . . . . . . . . . . 30-Jul-1999 13:14Sample Sample ID . . . . . . . . . . . O2 Entry type . . . . . . . . . . . Weight Lower limit [g] . . . . . . . 0.0 Upper limit [g] . . . . . . . 5.0 Molar mass M . . . . . . . . . . 32.0 Equivalent number z . . . . . . 1 Titration stand . . . . . . . . Stand 1 Temperature sensor . . . . . . . ManualDispense Titrant . . . . . . . . . . . . Chloroform/AA Concentration [mol/L] . . . . . 0.1 Volume [mL] . . . . . . . . . . 20Instruction Text . . . . . . . . . . . . . . Add 1 mL KI solutionStir Speed [%] . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . 300Instruction Text . . . . . . . . . . . . . . Add 50 mL destilled waterEQP titration Titrant/Sensor Titrant . . . . . . . . . . . Na2S2O3 Concentration [mol/L] . . . . 0.01 Sensor . . . . . . . . . . . DM140 Unit of meas . . . . . . . . mV Predispensing . . . . . . . . . No Titrant addition . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . 0.2 Measure mode . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . 200.0 Steepest jump only . . . . . No Range . . . . . . . . . . . . No Tendency . . . . . . . . . . Negative Termination at maximum volume [mL] . . . 20.0 at potential . . . . . . . . No at slope . . . . . . . . . . No afternumber EQPs . . . . . . Yes n = . . . . . . . . . . . 1 comb. term. conditions . . . No Evaluation Procedure . . . . . . . . . . Standard Potential 1 . . . . . . . . . No Potential 2 . . . . . . . . . No Stop for reevaluation . . . . NoCalculation Formula . . . . . . . . . . . . R=VEQ Constant . . . . . . . . . . . . Decimal places . . . . . . . . . 3 Result unit . . . . . . . . . . mL Result name . . . . . . . . . . Blank Statistics . . . . . . . . . . . YesAuxiliary value ID . . . . . . . . . . . . . . . Blank Peroxide Value Formula . . . . . . . . . . . . H1=xReport Output . . . . . . . . . . . . Printer Results . . . . . . . . . . . . No All results . . . . . . . . . . Yes Raw results . . . . . . . . . . Yes Table of measured values . . . . Yes Sample data . . . . . . . . . . Yes E - V curve . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . Yes

66

M238

Oxidazable substances

5 mL 20% sulphuric acid, H2SO4

Potassium permanganate KMnO4,c(KMnO4) = 0.1 mol/L

DL55+, DL58, DL70ES/DL7DH100 Heating System,Balance, printer

MnO4- + 5e- + 8H2O = Mn2- + 12H2O

Glass titration beaker ME-101446 2 (1) Additional buretteCable DH100-Titrator(DL5x: 51 07424, DL7x: 51 108404)

METTLER TOLEDO

Aqueous acid solutions containingmetal ions.

Wastedisposal

Preparation and ProceduresWaste water (low degree), 50 mLSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM140-SCIndication

Determination of Permanganate Index in Waste Water

1) The sample is heated for at least 10 minutes at more than85°C.

2) The solution is acidified by adding manually (or with aburette) 5 mL 20 % sulphuric acid.

3) 2 mL 0.1 KMnO4 are dispensed with a burette. After waiting150 s, an EP titration is started. The time delay is set to 60 saccording to the application.

Note:1) The titer determination is performed using sodium oxalate.ca. 25-40 mg are dissolved in 50 mL 5% sulfuric acid andwormed to 80°C, since the titration runs slowly at room T.(See application no. M527).

2) Do not dip the tip of the burettes into the sample solution toavoid diffusion into sample solution.

1) The permanganate index is the amount of oxygen whichcorresponds to the equivalent of permanganate ions consumendin the reaction. It is an indicative parameter for tjhe amounf otoxidazable substances, and therefore an indication for hewpollution of waters.

2) Method M238 is a simplified version of the procedure basedon on DIN 38409-H5 (ISO 8467).

3) This method is a more easier and straightforward method asth COD determination. Since the oxidative power is lowercompared to COD, not all substances are oxidazed.

Literature:DIN 38409-H5, ISO 8467

Remarks

R= (QDISP+Q)*C/mC= 1000 , mmol/L

DL7x: U ; instead of m

Calculation

Determination of permanganate index in waste water by titration with potassium permanganate.This application is especially suited for low content of oxidazable substances.

Standard Sodium oxalate, Na2C2O4 (see M527)

Ch. Walter, A. AichertAuthor

67


METTLER DL77 Titrator V3.1 Mettler-Toledo AG IC113 Market Support Laboratory

Method 238 KMnO4 Number 12-Jan-1994 11:38UserMeasured 12-Jan-1994 12:06

RESULTS


1/1 COOH 50.0 mL Fixed volume U R1 = 7.900 mmol/L KMnO 4 Number 1/2 COOH 50.0 mL Fixed volume U R1 = 2.800 mmol/L KMnO 4 Number 1/3 COOH 50.0 mL Fixed volume U R1 = 7.700 mmol/L KMnO 4 Number

STATISTICS Number results n = 3 Mean value x = 7.800 mmol/L KMnO 4 Number Standard deviation s = 0.100000 mmol/L KMnO 4 Number Rel. standard deviation srel = 1.282 % Outlier test: no outliers!

Titration curve

Results

68

Method 238 KMnO4 Number Version 12-Jan-1994 11:38

Title Method ID . . . . . . . . . . . . . 238 Title . . . . . . . . . . . . . . . KMnO4 Number Date/time . . . . . . . . . . . . . 12-Jan-1994 11:38Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 100.0 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . TEMP ATemperature Sensor . . . . . . . . . . . . . . . TEMP A Unit of meas. . . . . . . . . . . . °C dT [°C,°F, K] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . . . . 2.0 t(min) mode . . . . . . . . . . . . T larger Set Set value [°C,°F, K] . . . . . . 85.0 t(max) [s] . . . . . . . . . . . . . 600.0Dispense Titrant . . . . . . . . . . . . . . KMnO4

Concentration [mol/L] . . . . . . . 0.1 Volume [mL] . . . . . . . . . . . . 2Measure Sensor . . . . . . . . . . . . . . . DM140-SC Unit of meas. . . . . . . . . . . . mV dE [mV] . . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . . . 1.0 t(min) mode . . . . . . . . . . . . Fix Set value [°C,°F, K] . . . . . . 150.0 t(max) [s] . . . . . . . . . . . . . 150.0Titration Titrant . . . . . . . . . . . . . . KMnO4

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EP Predispensing . . . . . . . . . . mL Volume [mL] . . . . . . . . . 0 Titrant addition . . . . . . . . Continuous Control band [mV, pH, ...] . . 100.0 Time delay [s] . . . . . . . . 60.0 dV [mL] . . . . . . . . . . . 0.05 End point mode . . . . . . . . . EPA Potential [mV, pH, ...] . . . 1150.0 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 10.0Calculation Result name . . . . . . . . . . . . KMnO4 Number Formula . . . . . . . . . . . . . . R=(QDISP+Q)*C/U Constant . . . . . . . . . . . . . . C=1000 Result unit . . . . . . . . . . . . mmol/L Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Method

69

M239

Oxidazable organic substances

10 mL potassium dichromate, K2Cr2O7

c(1/6 K2Cr2O7) = 0.12 mol/L30 mL 0.1 mol/L Ag2SO4/H2SO4

FAS, (NH4)2Fe(II)(SO4)2

c(FAS)= 0.12 mol/L;

DL50Graphix, DL5x, DL70ES/DL77Rondo 60, Rondo COD Set, magneticstirrer for Rondo 60.

Cr2O72- + 6Fe2+ + 14H+ = 2Cr3+ + 6Fe3+ + 7H2O

2 Cr3+ = 2 Cr3+ + 6 e-

1.5 mol O2 = 6 mol 1/6Cr2O72- = 6mol FAS

1 mol O2 = 4 mol 1/6Cr2O72- = 4 mol FAS

Therefore: z = 4

Heater with reflux condenser (thirdparty), 1 additional burette DV1010(DL7x: two additional burettes),Balance, Printer

METTLER TOLEDO

The waste contains organic solventsand is disposed accordingly.

Wastedisposal

Preparation and ProceduresWaste water, 20 mL(Or: KHP solution as standard)

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM144-SCIndication

Chemical Oxygen Demand (COD) of Waste Water

1) The sample preparation is performed automatically on theRondo 60 sample changer using method 4001:1.1 Add magnetic stirrer into the COD glass tube (boiling add).1.2 20 mL waste water are added1.3 Add 10 mL 0.12 molL 1/6 K2Cr2O7 containing Hg2SO4 tomask chloride (conc.: 0.4g/20 mL, commercially available).1.4 30 mL Ag2SO4/H2SO4 are slowly added by a burette.Be careful: Heat is developed !2) The COD glass tubes are brought to the digestor for heating.The sample solutions are boiled at 148 +/- 3°C for 2 hours.Afterwards, the COD tubes are let to cool down to at least 60°C.3) The condenser is rinsed with distilled water, and the tubesare filled with distilled water up to 100 mL. The tubes are cooleddown to room temperature and placed on the sample changerrack. Excess dichromate solution is titrated with FAS and theresults expressed as mg O2/L.The whole COD procedure is tested with 20 mL potassiumhydrogen phtalate KHP solution (COD = 200 +/- 8 mg O2/L).Preparation: KHP is dried at 105°C for 2 hours. 0.17 g KHP aredissolved in some water in a 1 L volumetric flask. Add 5 mLconcentrated H2SO4, and fill up to 1000 mL. The solutionremains stable for 1 week when kept cool.

1) Chemical Oxygen Demand (COD) is a summary value thatindicates the water quality in the environmental protection field.By means of COD back titration the quantity of oxidazableorganic matter -expressed as the equivalent amount of oxygen-is determined by oxidation with potassium dichromate. First theamount of dichromate (without sample) is determined usingmethod 4002 and stored as auxiliary value. After oxidation thesample solution is titrated with dichromate using method 4003.2) The COD value is proportional to the total amount of organicoxidazable matter including non- or hardly biodegradablematter. Therefore all inorganic components that could beoxidized too have to be masked during or removed beforeoxidation step (masking agent: mercury(II) sulfate).3) The same special flask of the Rondo 60 COD set is used forthe sample preparation (oxidation step) and titration.4) The titer of FAS must be checked daily.5) For accurate results, it is recommended to use distilled waterinstead of deionized water.

Literature:DIN 38409 part 4, H4

Remarks

COD determination (Method 4003)R = (H18-Q)*C/mC = M*1000/z , mg O2/L

Back value determination (4002)R = QQ is stored as auxiliary value H18

Calculation

Determination of the COD value in waste water according to DIN 38409 part 4, H4

Standard K2Cr2O7 (see application M548)

Peter Burri Author

70


METTLER TOLEDO DL58 Titrator V2.3 Titration Basic Course DL Basic Course Market Support Analytical

Method 4003 COD Determination 10-May-2000 16:36 Measured 10-May-2000 16:46 User PB

ALL RESULTS


1 8.0mL FAS 20.0 mL R1 = 427.828 mg O2/L COD R2 = 1.532 mL FAS consumed 2 8.0mL FAS 20.0 mL R1 = 427.682 mg O2/L COD R2 = 1.535 mL FAS consumed 3 8.0mL FAS 20.0 mL R1 = 428.336 mg O2/L COD R2 = 1.523 mL FAS consumed

STATISTICS Number of results R1 n = 3 Mean value x = 427.948 mg O2/L COD Standard deviation s = 0.3432 mg O2/L COD Rel. standard deviation srel = 0.080 %

Number of results R2 n = 3 Mean value x = 1.530 mL Standard deviation s = 0.00626 mL Rel. standard deviation srel = 0.409 %

Titration curve

Results

71

Method 4003 COD Determination Version 10-May-2000 16:36

Title Method ID . . . . . . . . . . . 4002 Title . . . . . . . . . . . . . COD Determination Date/time . . . . . . . . . . . 10-May-2000 16:36Sample Sample ID . . . . . . . . . . . Effluent Entry type . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . 20.0 Molar mass M . . . . . . . . . . 32.0 Equivalent number z . . . . . . 4 Titration stand . . . . . . . . ST20A Pump . . . . . . . . . . . . No Pump . . . . . . . . . . . . No Rinse . . . . . . . . . . . . Yes Solvent . . . . . . . . . H2SO4 5% Volume [mL] . . . . . . . 20.0 Conditioning . . . . . . . . No Temperature sensor . . . . . . . ManualStir Speed [%] . . . . . . . . . . . 22 Time [s] . . . . . . . . . . . . 25EQP titration Titrant/Sensor Titrant . . . . . . . . . . . (NH4)2Fe(II)(SO4)2

Concentration [mol/L] . . . . 0.12 Sensor . . . . . . . . . . . DM144 Unit of meas . . . . . . . . mV Predispensing . . . . . . . . . to volume Volume [mV] . . . . . . . . . 0.5 Wait time [s] . . . . . . . . 10 Titrant addition . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . 6.0 dV(min) [mL] . . . . . . . . 0.05 dV(max) [mL] . . . . . . . . 0.5 Measure mode . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . 200.0 Steepest jump only . . . . . No Range . . . . . . . . . . . . No Tendency . . . . . . . . . . Negative Termination at maximum volume [mL] . . . 15.0 at potential . . . . . . . . No at slope . . . . . . . . . . No after number EQPs . . . . . . Yes n = . . . . . . . . . . . 1 comb. term. conditions . . . No Evaluation Procedure . . . . . . . . . . Standard Potential 1 . . . . . . . . . No Potential 2 . . . . . . . . . No Stop for reevaluation . . . . Yes Condition . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . R=(H18-Q)*C/m Constant . . . . . . . . . . . . C=M*1000/z Decimal places . . . . . . . . . 3 Result unit . . . . . . . . . . mg O2/L Result name . . . . . . . . . . COD Statistics . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . Decimal places . . . . . . . . . 3 Result unit . . . . . . . . . . mL Result name . . . . . . . . . . FAS consumed Statistics . . . . . . . . . . . YesReport Output . . . . . . . . . . . . Printer Results . . . . . . . . . . . . No All results . . . . . . . . . . Yes Raw results . . . . . . . . . . No Table of measured values . . . . Yes Sample data . . . . . . . . . . No E - V curve . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . No log dE/dV - v curve . . . . . . No E - t curve . . . . . . . . . . No V - t curve . . . . . . . . . . No dV/dt - t curve . . . . . . . . No

MethodMethod 4003:similar to 4002, an additional auxiliary function is used tostore the result in mmol (Q) as auxiliary value H18

Method 4001 COD Preparation Version 08-May-2000 17:12

Title Method ID . . . . . . . . . . . 4001 Title . . . . . . . . . . . . . COD Preparation Date/time . . . . . . . . . . . 08-May-2000 17:12Sample Sample ID . . . . . . . . . . . Chemicals Entry type . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . 20.0 Molar mass M . . . . . . . . . . 58.43 Equivalent number z . . . . . . 1 Titration stand . . . . . . . . ST20A Pump . . . . . . . . . . . . No Pump . . . . . . . . . . . . No Rinse . . . . . . . . . . . . Yes Solvent . . . . . . . . . H2SO4 5% Volume [mL] . . . . . . . 2.0 Conditioning . . . . . . . . No Temperature sensor . . . . . . . ManualDispense Titrant . . . . . . . . . . . . 1/6 K2Cr2O7

Concentration [mol/L] . . . . . 0.12 Volume [mL] . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . 25 Time [s] . . . . . . . . . . . . 20EQP titration Titrant/Sensor Titrant . . . . . . . . . . . H2SO4/Ag2SO4

Concentration [mol/L] . . . . 0.1 Sensor . . . . . . . . . . . DM144 Unit of meas . . . . . . . . mV Predispensing . . . . . . . . . No Titrant addition . . . . . . . . Incremental dV [mL] . . . . . . . . . . . 0.5 Measure mode . . . . . . . . . Timed increment dt [s] . . . . . . . . . . . 10.0 Recognition Threshold . . . . . . . . . . 400.0 Steepest jump only . . . . . No Range . . . . . . . . . . . . No Tendency . . . . . . . . . . None Termination at maximum volume [mL] . . . 30.0 at potential . . . . . . . . No at slope . . . . . . . . . . No after number EQPs . . . . . . No Evaluation Procedure . . . . . . . . . . Standard Potential 1 . . . . . . . . . No Potential 2 . . . . . . . . . No Stop for reevaluation . . . . NoCalculation Formula . . . . . . . . . . . . R=VEND Constant . . . . . . . . . . . . Decimal places . . . . . . . . . 3 Result unit . . . . . . . . . . mL Result name . . . . . . . . . . H2SO4

Statistics . . . . . . . . . . . NoReport Output . . . . . . . . . . . . Printer Results . . . . . . . . . . . . No All results . . . . . . . . . . Yes Raw results . . . . . . . . . . No Table of measured values . . . . No Sample data . . . . . . . . . . No E - V curve . . . . . . . . . . No dE/dV - V curve . . . . . . . . No d2E/dV2 - V curve . . . . . . . No log dE/dV - v curve . . . . . . No E - t curve . . . . . . . . . . No V - t curve . . . . . . . . . . No dV/dt - t curve . . . . . . . . No

72

M517

Acidic components

Toluene/2-propanol/water 500:495:5

Potassium hydroxide in 2-propanolc(KOH) = 0.1 mol/L;

DL50Graphix, DL53/55/58,DL70ES/77Sample changer, Printer

Titration beaker ME-101974Pump ME-65241

METTLER TOLEDO

Aromatic organic wasteWastedisposal

Preparation and Procedures60 mL Solvent 664Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113Indication

Blank determination according to ASTM D664-89

1) The blank determination of solvent 664 used for AN-Analysis(toluene/2-propanol/water 500:495:5) is done automaticallywith the sample changer.

2) 60 mL solvent 664 are added with the pump. After everytitration the electrode is conditioned in water for 5 minutes andthen rinsed with solvent 664.

1) The analysis is performed by placing the followingsuccession of beakers on the sample turntable:1.1 An empty beaker followed by a beaker with 60 mL deion.water for conditioning (indicated with a yellow clip).1.2 Before starting the method the alkaline buffer potential(buffer B) must be entered as endpoint in the functionTITRATION.1.3 The result of this blank determination is stored as auxiliaryvalue H10. It is used for calculation in the acid numberdetermination (method 90019).

Literature:ASTM D664-89 (see www.astm.org)Application brochrue 3, "TAN and TBN", ME-724559

Remarks

R = Q ; mmolR is stored as auxiliary value H10.

Calculation

A method for the determination of the blank value for a acid number analysis according to ASTM D664-89.


A. Aichert, A. LogeanAuthor

73


METTLER TOLEDO DL53 Titrator V1.0 Mettler-Toledo AG 010 Market Support Laboratory

Method 90017 Blindwert AN ASTM D664 01-Jul-1995 12:00Measured 20-Jul-1995 15:04User

RESULTS


1 60.0 mL R1 = 0.0044 mmol Blank 2 60.0 mL R1 = 0.0041 mmol Blank 3 60.0 mL R1 = 0.0043 mmol Blank

STATISTICS Number results R1 n = 3 Mean value x = 0.0043 mmol Blank Standard deviation s = 0.00015 mmol Blank Rel. standard deviation srel = 3.559 %

AUXILIARY VALUE New value H10 = 0.00429 Blank AN ASTM D

Titration curve

Results

74

Method 90017 Blank AN ASTM D664 Version 01-Jul-1995 12:00

Title Method ID . . . . . . . . . . . . . 00017 Title . . . . . . . . . . . . . . . Blank AN ASTM D664 Date/time . . . . . . . . . . . . . 01-Jul-1995 12:00Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 60.0 Molar mass M . . . . . . . . . . . . 100.0 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . ST20A Pump . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . Solvent 664 Volume [mL] . . . . . . . . . 60.0 Rinse . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . Solvent 664 Volume [mL] . . . . . . . . . 20.0 Conditioning . . . . . . . . . . Yes Time [s] . . . . . . . . . . . 300 Rinse . . . . . . . . . . . . Yes Solvent . . . . . . . . . . Solvent 664 Volume [mL] . . . . . . . . 20.0 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10EP titration Titrant/Sensor Titrant . . . . . . . . . . . . . KOH (i-PrOH) Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 4.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.05 dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 6.0 t(min) [s] . . . . . . . . . . . 6.0 t(max) [s] . . . . . . . . . . . 30.0 End point . . . . . . . . . . . . . EP absolute Potential [mV,pH,..] . . . . . . -143 Tendency Tendency . . . . . . . . . . . . Negative Termination Maximum volume [mL] . . . . . . . 1.0 Delay [s] . . . . . . . . . . . . 0Calculation Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Blank Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoAuxiliary value ID . . . . . . . . . . . . . . . . . Blank AN ASTM D664 Formula . . . . . . . . . . . . . . H10=x

MethodReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of measured values . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . No dE/dV - V curve . . . . . . . . . . No d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . .

75

M518

Alkaline components

toluene/2-propanol/chloroform/water100:100:100:3

Hydrochloric acid in 2-propanol c(HCl)= 0.1 mol/L

DL50Graphix, DL53/55/58,DL70ES/77Rondo 60

Titration beaker ME-101974,Printer

METTLER TOLEDO

The conditioning beakers contain amixture of water/aromatic organicsolvents. For waste disposal, separatewater and solvent.

Wastedisposal

Preparation and Procedures60 mL Solvent 4739Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113Indication

Blank determination according to ASTM D4739-92

1) The blank determination of solvent 4739(toluene/2-propanol/chloroform/water 100:100:100:3) is doneautomatically with the sample changer.

2) 60 mL solvent 4739 are added with the pump. After everytitration the electrode is conditioned in water for 5 minutes andthen rinsed with solvent 4739.

1) The analysis is performed by placing the followingsuccession of beakers on the sample turntable:1.1 An empty beaker followed by a beaker with 60 mL deion.water for conditioning (indicated with a yellow clip).1.2 Before starting the method, the acidic buffer potential (bufferA) must entered as endpoint in the function TITRATION.

2) The result of this blank determination is stored as auxiliaryvalue H11. It is used for calculation in the base numberdetermination (method 90020).

Literature:ASTM D4789-92 (www.astm.org)Application brochure 3, "TAN and TBN", ME-724559

Remarks

R = Q ; mmol

R is stored as auxiliary value H11

Calculation

A method for the determination of the blank value for a Base Number analysis according to ASTMD4739-92.

Standard KOH 0.1 mol/L


76



Method 90018 Blank BN ASTM D4739 01-Jul-1995 12:00Measured 18-Jul-1995 15:15User

RESULTS


1 60.0 mL R1 = 0.0011 mmol Blank value 2 60.0 mL R1 = 0.0010 mmol Blank value 3 60.0 mL R1 = 0.0011 mmol Blank value

STATISTICS Number results R1 n = 3 Mean value x = 0.0011 mmol Blank value Standard deviation s = 0.00004 mmol Blank value Rel. standard deviation srel = 3.467 %

AUXILIARY VALUE New value H11 = 0.00108 Blank value BN

Titration curve

Results

77

Method 90018 Blank BN ASTM D4739 Version 01-Jul-1995 12:00

Title Method ID . . . . . . . . . . . . . 90018 Title . . . . . . . . . . . . . . . Blank BN ASTM D4739 Date/time . . . . . . . . . . . . . 01-Jul-1995 12:00Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 60.0 Molar mass M . . . . . . . . . . . . 100.0 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . ST20A Pump . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . Solvent 4739 Volume [mL] . . . . . . . . . 60.0 Rinse . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . Solvent 4739 Volume [mL] . . . . . . . . . 20.0 Conditioning . . . . . . . . . . Yes Time [s] . . . . . . . . . . . 300 Rinse . . . . . . . . . . . . Yes Solvent . . . . . . . . . . Solvent 4739 Volume [mL] . . . . . . . . 20.0 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10EP titration Titrant/Sensor Titrant . . . . . . . . . . . . . HCl (i-PrOH) Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 4.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.05 dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 6.0 t(min) [s] . . . . . . . . . . . 30.0 t(max) [s] . . . . . . . . . . . 90.0 End point . . . . . . . . . . . . . EP absolute Potential [mV,pH,..] . . . . . . 154 Tendency Tendency . . . . . . . . . . . . Positive Termination Maximum volume [mL] . . . . . . . 1.0 Delay [s] . . . . . . . . . . . . 0Calculation Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Blank value Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoAuxiliary value ID . . . . . . . . . . . . . . . . . Blank value BN D4739 Formula . . . . . . . . . . . . . . H11=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of measured values . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . No dE/dV - V curve . . . . . . . . . . No d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No

Method

78

M519

Acidic components

ASTM 664 solventToluene/2-propanol/water 500:495:5

Potassium hydroxide in 2-propanolc(KOH) = 0.1 mol/L;

DL50Graphix, DL53/55/58, DL7xRondo 60,

Titration beaker ME-101974balance, printer

METTLER TOLEDO

Aromatic organic waste. Theconditioning beakers contain a mixtureof water and organic solvents.

Wastedisposal

Preparation and Procedures1 - 20 g OilSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

AN (acid number) according to ASTM D664-89

1) Weigh in a well homogenised oil sample in the titrationbeaker and place it on the sample changer.

2) The 60 mL solvent 664 needed to dissolve the sample areadded automatically with the pump. The pump also rinses withsolvent 664 after titration and conditioning are done.

To proceed with this determination, the following steps areneeded:

1. Determination of the alkaline buffer value (buffer B).2. Blank determination of solvent 664 (method 90017).3. Enter the buffer B value in the function TITRATION of ANdetermination method 90019 (Parameter: evaluation, as"potential 1" and also as "termination at potential").

General procedure:1. Titer det. of 0.1 mol/L KOH 0.1 with KHP2. Determination of the alkaline buffer value (buffer B)3. Blank determ. of Solvent 664 (M517, Method 90017)4. Determ. of the base number (AN) (M519, Method 90019)

Acid number according to ASTM D664-89:Consumption of mg KOH/g oil to buffer value B or to the EQPnearest to the buffer value B.

Titration parameters:The titration parameters correspond exactly to the standard ASTMD664-89:

1. Titrant addition: max. speed 0.2 mL/min2. dE< 30 mV/0.1 mL —> Increment = 0.1 mL3. dE> 30 mV/0.1 mL —> Increment = 0.05 mL4. The titration will be terminated if the potential is below buffervalue B and the change is smaller than 50 mV/mL KOH.

ConditioningAfter every titration the electrode is conditioned in water for 5minutes and then rinsed with solvent 664. With this method theconditioning proceeds automatically, if the sample changerholds a conditioning beaker with 60 mL deion. water after everysample.

Literature:ASTM D664-89 (see www,astm.org)Application brochure 3, "TAN and TBN", ME-724559

Remarks

R1 = consumption of mg KOH/g oil to thebuffer value B

R2 = consumption of mg KOH/g oil to EQPnearest to the buffer value B

If there is no EQP, the result is negative.(Blank value of the solvent)

Calculation

Method for the determination of AN (Acid Number) according to ASTM D664-89

Standard Potassium hydrogen phthalate, KHP


79



Method 90019 AN ASTM D664 01-Jul-1995 12:00Measured 21-Jul-1995 19:47User

RESULTS


1 Oil 7.275 g R1 = 1.83 mg KOH/g AN (Buffer B) R2 = -0.03 mg KOH/g AN (EQP) 2 Oil 6.768 g R1 = 1.81 mg KOH/g AN (Buffer B) R2 = -0.04 mg KOH/g AN (EQP) 3 Oil 6.975 g R1 = 1.81 mg KOH/g AN (Buffer B) R2 = -0.03 mg KOH/g AN (EQP) 4 Oil 6.706 g R1 = 1.79 mg KOH/g AN (Buffer B) R2 = -0.04 mg KOH/g AN (EQP) 5 Oil 7.227 g R1 = 1.73 mg KOH/g AN (Buffer B) R2 = -0.03 mg KOH/g AN (EQP)

STATISTICS Number results R1 n = 5 Mean value x = 1.79 mg KOH/gAN (Buffer B) Standard deviation s = 0.03513 mg KOH/gAN (Buffer B) Rel. standard deviation srel = 1.960 %

Titration curve

Results

80

Method 90019 AN ASTM D664 Version 01-Jul-1995 12:00

Title Method ID . . . . . . . . . . . . . 90019 Title . . . . . . . . . . . . . . . AN ASTM D664 Date/time . . . . . . . . . . . . . 01-Jul-1995 12:00Sample Sample ID . . . . . . . . . . . . . Oil Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.1 Upper limit [g] . . . . . . . . . 20.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . ST20A Pump . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . Solvent 664 Volume [mL] . . . . . . . . . 60.0 Rinse . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . Solvent 664 Volume [mL] . . . . . . . . . 20.0 Conditioning . . . . . . . . . . Yes Time [s] . . . . . . . . . . . 300 Rinse . . . . . . . . . . . . Yes Solvent . . . . . . . . . . Solvent 664 Volume [mL] . . . . . . . . 20.0 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . KOH (i-PrOH) Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 0.2 Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 30.0 dV(min) [mL] . . . . . . . . . . 0.05 dV(max) [mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 6.0 t(min) [s] . . . . . . . . . . . 30.0 t(max) [s] . . . . . . . . . . . 90.0 Recognition Threshold . . . . . . . . . . . . 250.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . Yes Limit A [mV,pH,...] . . . . . -20 Limit B [mV,pH,...] . . . . . -300 Tendency . . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . Yes Potential [mV,pH,..] . . . . . -150 at slope . . . . . . . . . . . . Yes Slope [mV,pH,.../mL] . . . . . 50.0 after number EQPs . . . . . . . . No comb. termination conditions . . Yes Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . Yes Pot. 1 [mV,pH,...] . . . . . . -150 Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . No

MethodCalculation Formula . . . . . . . . . . . . . . R1=(QP1-H10)*M/m Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg KOH/g Result name . . . . . . . . . . . . AN (Buffer B) Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=(Q(EPOT~P1)-H10)*C2 Constant . . . . . . . . . . . . . . C2=M/m Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg KOH/g Result name . . . . . . . . . . . . AN (EQP) Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes Table of measured values . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . No d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

81

M520

Basic components

ASTM 4739 solventToluene/2-propanol/chloroform/water100:100:100:3

Hydrochloric acid in 2-propanol c(HCl)= 0.1 mol/L;

DL50Graphix, DL53/55/58,Rondo 60 Sample changer

Titration beaker ME-101974Balance, printer

METTLER TOLEDO

Separate water and halogenatedorganic solvent before disposing.

Wastedisposal

Preparation and Procedures1 - 20 g OilSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

BN (base number) ASTM D4739-92

1) Weigh in a well homogenized oil sample in the titrationbeaker and place it on the sample changer.

2) The 60 mL solvent 4739 needed to dissolve the sample areadded automatically with the pump. The pump also rinses withsolvent 4739 after titration and conditioning are done.

To proceed with this determination, the following steps areneeded:1. Determination of the acid buffer value (buffer A)2. Blank of solvent 4739 (method 90018)3. Enter the buffer A value in the function TITRATION of method90020 (parameter: evaluation, as "potential 1"; also the rangefor the EQP recognition, "buffer value A +100 mV", and also astermination at potential, "buffer value A + 120 mV").

General procedure:1. Titer det. of 0.1 mol/L HCl with standardized KOH 0.1 mol/L2. Determination of the acidic buffer value (buffer A)3. Blank determ. of Solvent 4739 (M518, Method 90018)4. Determ. of the base number (BN) (M520, Method 90020)

Base number according to ASTM D4739-92Consumption of mg KOH/g oil to buffer value A or to the EQP inthe range "buffer value A + 100 mV"

Titration parametersThe titration parameters correspond exactly to the standard ASTMD4739:1. Titrant addition 0.1 mL every 90 seconds.2. The titration will be terminated when the potential is 120 mVabove buffer value A.

ConditioningAfter every titration the electrode is conditioned in water for 5minutes and then rinsed with solvent 4739. With this methodthe conditioning is automatically proceeded, if on the samplechanger after every sample a conditioning beaker with 60 mLdeion. water is placed.

Literature:ASTM D4739-92 (www.astm.org)Application brochure 3, "TAN and TBN", ME-724559

Remarks

R1 = consumption of mg KOH/g oil to thebuffer value A

R2 = consumption of mg KOH/g oil to EQPnearest to the buffer value A

If there is no EQP, the result is negative.(Blank value of the solvent).

Calculation

Method for the determination of BN (Base Number) according to ASTM D4739-92

Standard


82



Method 90020 BN ASTM D4739 01-Jul-1995 12:00Measured 18-Jul-1995 23:44User

RESULTS


1 Oil 1.7955 g R1 = 9.90 mg KOH/g BN (buffer A) R2 = 10.88 mg KOH/g BN (EQP) 2 Oil 2.1974 g R1 = 9.79 mg KOH/g BN (buffer A) R2 = 10.92 mg KOH/g BN (EQP) 3 Oil 1.9269 g R1 = 9.71 mg KOH/g BN (buffer A) R2 = 10.86 mg KOH/g BN (EQP) 4 Oil 2.1927 g R1 = 9.63 mg KOH/g BN (buffer A) R2 = 10.81 mg KOH/g BN (EQP) 5 Oil 1.8911 g R1 = 9.67 mg KOH/g BN (buffer A) R2 = 10.83 mg KOH/g BN (EQP)

STATISTICS Number results R1 n = 5 Mean value x = 9.74 mg KOH/gBN (buffer A) Standard deviation s = 0.10709 mg KOH/gBN (buffer A) Rel. standard deviation srel = 1.099 %

STATISTICS Number results R2 n = 5 Mean value x = 10.86 mg KOH/gBN (EQP) Standard deviation s = 0.04364 mg KOH/gBN (EQP) Rel. standard deviation srel = 0.402 %

Titration curve

Results

83

Method 90020 BN ASTM D4739 Version 01-Jul-1995 12:00

Title Method ID . . . . . . . . . . . . . 90020 Title . . . . . . . . . . . . . . . BN ASTM D4739 Date/time . . . . . . . . . . . . . 01-Jul-1995 12:00Sample Sample ID . . . . . . . . . . . . . Oil Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.1 Upper limit [g] . . . . . . . . . 20.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . ST20A Pump . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . Solvent 4739 Volume [mL] . . . . . . . . . 60.0 Rinse . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . Solvent 4739 Volume [mL] . . . . . . . . . 20.0 Conditioning . . . . . . . . . . Yes Time [s] . . . . . . . . . . . 300 Rinse . . . . . . . . . . . . Yes Solvent . . . . . . . . . . Solvent 4739 Volume [mL] . . . . . . . . 20.0 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . HCl (i-PrOH) Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 0.2 Titrant addition . . . . . . . . . . Incremental dV [mL] . . . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Time incremental dt [s] . . . . . . . . . . . . . 90.0 Recognition Threshold . . . . . . . . . . . . 200.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . Yes Limit A [mV,pH,...] . . . . . 154 Limit B [mV,pH,...] . . . . . 254 Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . Yes Potential [mV,pH,..] . . . . . 300 at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . Yes Pot. 1 [mV,pH,...] . . . . . . 154 Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . No

MethodCalculation Formula . . . . . . . . . . . . . . R1=(QP1-H11)*M/m Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg KOH/g Result name . . . . . . . . . . . . BN (buffer A) Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=(Q(EPOT~P1)-H11)*C2 Constant . . . . . . . . . . . . . . C2=M/m Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg KOH/g Result name . . . . . . . . . . . . BN (EQP) Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes Table of measured values . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . No d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

84

M057

Basic components

50 mL Solvent mixture(Acetic acid:chlorobenzene, 1:2)

0.1 mol/L HClO4 in glacial acetic acid,Sodium acetate in glacial acetic acidc(CH3COONa)= 0.1 mol/L

DL70ES, DL77;Rondo 60 Sample changer

100 mL beaker ME-101974,1 additional burette DV1010,10 mL syringe ME-71482

METTLER TOLEDO

Halogenated organic waste. Separatethe aquoeus pahse (upper) from theorganic phase (lower).

Wastedisposal

Preparation and ProceduresMotor oil, 0.1-20 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SC at Sensor 1Indication

TBN According to ASTM D 2896-85

1) The sample is weighed in a titration beaker and placed onthe sample changer rack.2) The solvent 2896 is automatically added by the pump(Function PUMP).

General procedure for direct titration :1. Blank determination of solvent 2896 (method 096B). Theblank is stored as auxiliary value H10 (mL)2. Titer determination of perchloric acid using KHP in solvent2896. The solvent blank H10 in mL has to be taken intoaccount for the titer determination (method 096C).3. The solvent blank value H10 (mL) is expressed in mmolusing the titer. The result is stored as auxiliary value H11.4. TBN determination (method 096A)

Note:If the direct titration cannot find an equivalence point, a backtitration has to be performed: a known amount HClO4 is addedto the sample, and the excess is titrated with sodium acetate.General procedure (back titration):1. Titer determination of sodium acetate with standardizedperchloric acid. Blank H11 must be taken into account in thecalculation for the titer: R=(QDISP-H11)/(VEQ*c)2. TBN determination by back titration. Blank H11 must betaken into account for the base number:R=(QDISP-H11-Q)*C/m

TBN:Consumption of perchloric acid until the inflection point. It isexpressed as the equivalent quantity t of mg KOH/g sample.

1) The blank of the solvent has to be determined regularly, atleast after preparing a new stock of solvent mixture.

2) After each titration the electrode is conditioned in water.

3) It is recommended to condition a spare electrode in water.This allows an alternating use of the electrodes or a quickreplacement.

4) ASTM D2896 specifies saturated sodium perchlorate in aceticacid as electrolyte. The replacement is straighforward.

5) The sample size is calculated according to the standard willgive a titrant consumption of about 5 mL.

6) Using the methods of this application note the titrations willtake about 10 to 15 minutes only.

7) KHP is dissolved externally in 50 mL solvent at 50°C usingan ultra sonic bath.

Literature: ASTM 2896-85 (www.astm.org)

Remarks

Base no. determination (096A):R = (Q-H11)*C/mC = M/z , where M = 56.1, z = 1mg KOH/g

Calculation

Method for the determination of TBN According to ASTM D 2896-85, in motor oil.This application does not replace the ASTM standard.

Standard KHP; HClO4 in glacial acetic acid

Urs BüchiAuthor

85


METTLER DL70 Titrator Mettler-Toledo AG Application Laboratory

96d ASTM D 2896-85 (direct) measured 11-11-1991 10:0808-11-1991 13:40 Titrator PT 7SW Version 2.0 User ub

RESULTS

No IDentification Weight Results

1/1 Oil 85/06 1.9882 g 12.78 mg KOH/g base number



STATISTICS Number results R1 n = 3 Mean value x = 12.74 mg KOH/g base number Standard deviation s = 0.039 mg KOH/g base number Rel. standard deviation srel = 0.309 %

Note:The same oil was titrated directly and by back titration.The results differ less than 1%.

Titration curve

Results

86

Method 096A ASTM D 2896-85 (direct) Version 08-Nov-1991 13:40

Title Method ID . . . . . . . . . . . . . 096A Title . . . . . . . . . . . . . . . ASTM D 2896-85 (direct) Date/time . . . . . . . . . . . . . 08-Nov-1991 13:40Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Weight m Lower limits[g] . . . . . . . . . 0.1 Upper limits[g] . . . . . . . . . 20.0 ID1 . . . . . . . . . . . . . . . . Oil Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1Pump Auxiliary reagent . . . . . . . . . AcOH-C6H5Cl 1:2 Volume [mL] . . . . . . . . . . . . 50.0Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60Titration Titrant . . . . . . . . . . . . . . HClO4 Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . 2.0 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . 30.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.05 dV(max) [mL] . . . . . . . 0.1 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 6.0 t(min) [s] . . . . . . . . . . 6.0 t(max) [s] . . . . . . . . . . 60.0 Threshold . . . . . . . . . . . 75.0 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . base number Formula . . . . . . . . . . . . . . R=(Q-H11)*C/m Constant . . . . . . . . . . . . . C=M/z Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . Q>0Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes Table of measured values . . . . . . Yes E - V curve . . . . . . . . . . . . YesRinse Auxiliary reagent . . . . . . . . . AcOH-C6H5Cl 1:2 Volume [mL] . . . . . . . . . . . . 15.0Conditioning Interval . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . 180 Rinse . . . . . . . . . . . . . . . Yes Auxiliary reagent . . . . . . . . AcOH-C6H5Cl 1:2 Volume [mL] . . . . . . . . . . . 15.0Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . YesConditioning Interval . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . 1

MethodTitle Method ID . . . . . . . . . . . . . 096B Title . . . . . . . . . . . . . . . Blank ASTM D2896-85 Date/time . . . . . . . . . . . . . 07-11-1991 11:26Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Fixed volume U Volume[mL] . . . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . Blank Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1Pump Auxiliary reagent . . . . . . . . . AcOH-C6H5Cl 1:2 Volume [mL] . . . . . . . . . . . . 50.0Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 30Titration Titrant . . . . . . . . . . . . . . HClO4 Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . INC dV(min) [mL] . . . . . . . . . 0.01 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . 6.0 t(min) [s] . . . . . . . . . . 6.0 t(max) [s] . . . . . . . . . . 60.0 Threshold . . . . . . . . . . . 500.0 Maximum volume [mL] . . . . . . . 0.5 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Blank volume Formula . . . . . . . . . . . . . . R=VEQ Result unit . . . . . . . . . . . . mL Decimal places . . . . . . . . . . 4Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . YesRinse Auxiliary reagent . . . . . . . . . AcOH-C6H5Cl 1:2 Volume [mL] . . . . . . . . . . . . 15.0Conditioning Interval . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . 30 Rinse . . . . . . . . . . . . . . . Yes Auxiliary reagent . . . . . . . . AcOH-C6H5Cl 1:2 Volume [mL] . . . . . . . . . . . 15.0Statistics Ri (i=index) . . . . . . . . . . . . R1Auxiliary value ID text . . . . . . . . . . . . . . Blank volume Formula . . . . . . . . . . . . . . H10=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . YesConditioning Interval . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . 1

Method 096C Titer of HClOO4 (0.1mol/L)

Calculation Result name . . . . . . . . . . . . Titer HClO4 Formula . . . . . . . . . . . . . . R=m/((VEQ-H10)*c*C) Result unit . . . . . . . . . . . . mLCalculation Result name . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . R2=H10*0.1*x Result unit . . . . . . . . . . . . mmoLAuxiliary value ID text . . . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . H11=R2

87

M058

Basic components

50 mL Solvent mixture 4739Isopropanol:H2O:Toluene:Chloroform(100:3:100:100)

HCl in isopropanol, c(HCl)=0.1 mol/LKOH in isopropanol, c(KOH)=0.1mol/L

DL70ES, DL77;Rondo 60 Sample changerBalance, printer

100 mL titration beaker ME-101974,1 additional DV90 drive1 additional DV1010 burette,10 mL syringe ME-71482

METTLER TOLEDO

Halogenated organic waste. Separatethe aqueous phase (upper) from theorganic phase (lower).

Wastedisposal

Preparation and ProceduresVarious oil, 0.1-20 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories


TBN According to ASTM D4739-87

1) The sample is weighed in a titration beaker and placed onthe sample changer rack.2) The solvent 4739 is automatically added by the pump(Function PUMP).

General procedure for direct titration :1. Titer determination of KOH in isopropanol dissolving 70-100mg KHP in 50 mL water (example: see M002, M027, M534).2. Titer determination of HCl in isopropanol using 5 mL of thestandardized KOH titrant solution (method 058C)3. Measurement of the buffer potentials A and B (058B)4. Blank determination for Base Number BN (with HCl, method058D) and Strong Base Number SBN (with KOH, 058E).5. Titration of oil samples (method 058A).

Note:1. The sample has to be homogenized well before weighing.Used oils might be heated to 50-60°C and may be filtered ifsediments are present.2. The values for buffer potentials from method 058B have to beentered manually into method 058A.3. The titration function in method 058A is terminated at a prestpotential. The end potentila corresponds to the acidic bufferpotential +200 mV (manual entry).

1) Standard ATM D4739-87 requires the evaluation o the resultat or beyond the acidic buffer potential. Therefoer, an evaluationwindow "EQP range" is activated. "Limit A" of this window is thepotential of the acidic buffer , "Limit B" corresponds to thispotential + 100 mV. The limits are entered manually.2) Calculations in method 058A:R1: Calculation of the SBN if there is a titrant consumption up tothe basic buffer (condition: VP1>0).R2: Calculation of the BN based on the titrant consumption up tothe acidic buffer, if no EQP was found (condition: VEQ=0).R3: BN based on a found EQP (condition: VEQ>0).3) A conditioning beaker with water is placed after each samplebeaker with 60 mL deionized water. Afterwards the electrode, thestirrer and the burette tip are rinsed with 20 mL solvent 4739before the analysis of the next sample.4) If no EQP occurs, the evaluation of the BN is made to theacidic buffer potential. The SBN corresponds to the consumptionto the basic buffer potential. The buffer potential determinationhas to be carried out every day or when using another electrode.5) At the end of the sample series two conditioning beakers arerequired to keep the electrode in deionized water.

Literature: ASTM 4739-87 (www.astm.org)Application brochure 20, ME-51725020Applications M576, M577, M584, M585, M586, M587, M588.

Remarks

Base no. determination (058A):R1 = (QP+H19)*C1/m ; mg KOH/gC1 = 56.1R2 = (QP2-H18)*C2/m ; mg KOH/gC2 = 56.1R3 = (Q-H18)*C3/m ; mg KOH/gC3 = 56.1

Calculation

Method for the determination of TBN according to ASTM D 4739-87 in motor oil.This application does not replace the ASTM standard.

Standard 1) KHP; 2) Stand. KOH in isopropanol

Urs BüchiAuthor

88


96d ASTM D 4739-87 measured 14-05-1992 12:3613-05-1992 13:36 Titrator GF121 PT2SW Version 2.0 User ub

RESULTS

No Identification Weight Results

1/1 Oil SAE 15W-40 1.2275 g 5.24 mg KOH/g base number



STATISTICS Number results R1 n = 0

STATISTICS Number results R2 n = 3 Mean value x = 5.03 mg KOH/g base number Standard deviation s = 0.185 mg KOH/g base number Rel. standard deviation srel = 3.673 %

STATISTICS Number results R3 n = 0

Sample Weight n Base Number (BN) Time 1. All tested sample did not have a SBN x s srel 2. All evaluation at the acidic bufferpotential (g) (mg KOH/g) (%) (min) Glossar: 2 2 6.53 0.071 1.08 31 TBN: Total Base Number 1 3 5.03 0.185 3.67 27 SBN: Strong Base Number 0.5 3 10.53 0.064 0.61 35 BN: Base Number 4 2 1.76 0.021 1.21 25

Buffer potential A and B:5 mL of the corresponding buffer stock solution are pipetted in the beakers on the sample changer. 60 mLsolvent are added automatically by a pump. The stock solutions can be kept for maximal two weeks.

Buffer stock solution A:100 mL isopropanol in 1 L volumetric flask, add 24.2 g 2,4,6-trimethyl pyridine ( γ−collidine), add 150 mLalcoholic 0.2 mol/L HCl, fill up to 1 L with isopropyl alcohol.

Buffer stock solution B:100 mL isopropanol in 1 L volumetric flask, add 27.8 g m-nitrophenol and dissolve, add 50 mL alcoholic 0.2mol/L KOH, fill up to 1 L with isopropyl alcohol.

Titration curve

Results

89

Method 058A ASTM D 4739-87 Version 13-05-1992 13:36

Title Method ID . . . . . . . . . . . . . 096A Title . . . . . . . . . . . . . . . ASTM D 4739-87 Date/time . . . . . . . . . . . . . 13-05-1992 13:36Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Weight m Lower limits[g] . . . . . . . . . 0.1 Upper limits[g] . . . . . . . . . 20.0 ID1 . . . . . . . . . . . . . . . . Oil Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1Pump Auxiliary reagent . . . . . . . . . solvent 4739 Volume [mL] . . . . . . . . . . . . 50.0Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60Titration Titrant . . . . . . . . . . . . . . HCl in i-PrOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . 0.2 Titrant addition . . . . . . . . INC dV [mL] . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . TFIX dt [s] . . . . . . . . . . . 90.0 Threshold . . . . . . . . . . . 50.0 EQP range . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . 151.0 Limit B [mV, pH,...] . . . . . 251.0 Maximum volume [mL] . . . . . . . 4.0 Termination at potential . . . . Yes Potential [mV, pH,...] . . . . 351.0 Evaluation procedure . . . . . . Standard Steepest jump only . . . . . . . Yes Buffer potential 1 . . . . . . . Yes Buffer potential 1 . . . . . . -153.5 Buffer potential 2 . . . . . . . Yes Buffer potential 2 . . . . . . 151.0Calculation Result name . . . . . . . . . . . . SBN Formula . . . . . . . . . . . . . . R=(QP1+H19)*C/m Constant . . . . . . . . . . . . . C=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . VP1>0Calculation Result name . . . . . . . . . . . . BN Formula . . . . . . . . . . . . . . R2=(QP2-H18)*C2/m Constant . . . . . . . . . . . . . C2=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . VEQ=0Calculation Result name . . . . . . . . . . . . Base Number Formula . . . . . . . . . . . . . . R3=(Q-H18)*C3/m Constant . . . . . . . . . . . . . C3=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . VEQ>0

MethodRinse Auxiliary reagent . . . . . . . . . Solvent 4739 Volume [mL] . . . . . . . . . . . . 20.0Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes Table of measured values . . . . . . Yes E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . YesConditioning Interval . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . 300 Rinse . . . . . . . . . . . . . . . Yes Auxiliary reagent . . . . . . . . Solvent 4739 Volume [mL] . . . . . . . . . . . 20.0Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . YesConditioning Interval . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . 10

Buffer determination ASTM D 4739-87:

Both buffers can be determined automatically with the samplechanger. First buffer A is measured, then buffer B. Theelectrode is conditioned before measuring the next buffer.

Buffer A -> R1 = E[1] = 151.001 mV -> stored as aux. valueH16Buffer B -> R2 = E[2] = -153.5489 mV -> stored as aux. valueH17

Blank determination for BN Method 058D:Solvent 4739-87 is dispensed automatically by a pump.Titrant:HCl in isopropanol, R = Q , stored as aux. value H18

Blank determination for SBN Method 058E:Solvent 4739-87 is dispensed automatically by a pump.Titrant:KOH in isopropanol, R = Q , stored as aux. value H19

90

M059

Acidic components

50 mL Solvent mixture 664,Toluene:water:isopropanol500:5:495

KOH in iopropanol (i-PrOH)HCl in i-PrOH c(HCl) = 0.1 mol/L

DL70ES/DL77;Rondo 60 sample changer,Balance, printer

Glass beaker ME101446,1 add. burette drive DV90, 1 add. glasburette Dv1010

METTLER TOLEDO

Separate organic phase from water.Disposal as aromatic organic solvent.

Wastedisposal

Preparation and ProceduresVarious oils 0.1 - 20 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories


TAN According to ASTM D 664-89

1) The sample is weighed in a titration beaker and placed onthesample changer rack.2) The solvent 664 is automatically added by the pump.(Function PUMP).

General procedure:1. Titer determination of KOH in isopropanol by dissolving70-100 mg in 50 mL water (example: M002, M027, M534).2. Titer determination of HCl in isopropanol using 5 mL ofstandardized KOH titrant soltuion (Method 059C).3. Measurement of the buffer potential A and B (059B).4. Blank determination for Acid Number AN (with KOH, method059D) and Strong Acid Number SAN (with HCl, method 059E).5. Titration of samples (method 059A).

Note:1. The sample has to be well homogenized before weighing.Used oils may be heated to 50 - 60 °C and filtered if sedimentsare present.2. The values for buffer potentials from method 059B have to beentered manually into method 059A.3. The difference between the two potential values must be at300 mV, otherwise the electrode must be checked.

1) Standard ASTM 664-89 requires the evaluation of the KOHconsumption at acid buffer potential (SAN) or the consumptionup to the EQP nearest to buffer B (AN).If no EQP can be found, then the consumption at buffer B (i.e.buffer potential 2) is evaluated (AN). Therefore, an evaluationwindow "EQP range" is activated. Within this range, the mostsignificant EQP only is evaluated ("steepest jump only yes").2) The limits of the EQP range in method 059A are set to ± 100mV of the buffer B (manual entry). The window can be modifiedas required by the user. The limits are entered manually.3) Calculations in method 059A:R1: Calculation of the SAN if there is a titrant consumption up tothe acidic buffer A (Condition: "VP1>0).R2: Calculation of the BN based on the titrant consumption up tobasic baffer B , if no EQP was found (Condition: "VEQ=0").R3: BN based on a found EQP (Condition: "VEQ>0").4) A conditioning beaker with 60 mL deion. water is placed aftereach sample on the sample tray ("conditioning interval = 1").5) The electrode, stirrer and burette tip are rinsed with 20 mLsolvent 664 before next sample. At the end of a series twoconditioning beakers are placed to store the electrode in water.

Literature:ASTM D664-89 (www.atm.org)Application brochure 20, ME51725020Applications M576, M577, M578, M579, M580, M581, M582

Remarks

Method 059A (Sample determination):R1=(QP1+H15)*C/m , C=56.1SAN (Strong acid number), mg KOH/gR2=(QP2-H14)*C2/m , C2=56.1AN (Acid number), mg KOH/gR3=(Q-H14)*C/m, C3=56.1AN (acid number), mg KOH/g

Calculation

Method for the determination of TAN According to ASTM D 664-89, in various oils.This application does not replace the ASTM standard.

Standard 1) KHP, 2) standard. KOH in i-PrOH

Urs BüchiAuthor

91


Sample Weight n Strong Acid Number (SAN) Acid Number (AN) Time [g] mg KOH/g sabs RSD[%] mg KOH/g sabs RSD[%] [min]MotorOil new ~5 3 no SAN - - 1.33 1) 0.036 2.71 31

Motor OilI used ~1 3 1.06 0.023 2.15 8.73 1) 0.032 0.36 27

Motor OilII used ~5 3 no SAN - - 2.93 1) 0.054 1.86 35

Arabianlight 15-20 3 no SAN - - 0.09 2) 0.005 5.12 25

HydraulicOil I 15-20 3 0.11 0.002 1.97 0.25 1) 0.004 1.56 15

HydraulicOil II 15-20 3 no SAN - - 0.06 2) 0.005 7.92 13

HydraulicOil III 15-20 3 no SAN - - 0.12 1) 0.001 0.85 18

Remarks1) Evaluation at the basic buffer potential; 2) Evaluation at found equivalence point; 3) i-PrOHisopropylalcoholexpected AN recommended sample weight[mg KOH/g] [g]0.05 - 1.9 201.0 - 4.9 55 - 4.9 1100 - 250 0.1

Buffer Stock Solution A (Acid buffer)Add 100 mL of i-PrOH in 1 L volumetric flask, add 24.2 g 2,4,6-trimethyl pyridine( γ-collidine), add 150 mLalcoholic HCl (c(HCl) = 0.2 mol/L), and fill up with i-PrOH to 1 L.

Buffer Stock Solution B (Basic buffer)Add 100 mL of i-PrOH in 1 L volumetric flask, add 27.8 g m-nitrophenol and dissolve, add 50 mL alcoholic KOH(c(KOH) = 0.2 mol/L), and fill up with i-PrOH to 1 L.Both stock solutions keep for maximal 2 weeks.

Titration curve

Results

92

Method 059A ASTM D 664-89 Version 07-May-1992 09:32

Title Method ID . . . . . . . . . . . . . 059A Title . . . . . . . . . . . . . . . ASTM D 664-89 Date/time . . . . . . . . . . . . . 07-May-1992 09:32Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Weight m Lower limits[g] . . . . . . . . . 0.1 Upper limits[g] . . . . . . . . . 20.0 ID1 . . . . . . . . . . . . . . . . Oil Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1Pump Auxiliary reagent . . . . . . . . . solvent 664 Volume [mL] . . . . . . . . . . . . 50.0Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60Titration Titrant . . . . . . . . . . . . . . KOH in i-PrOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . 0.2 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . 30.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . . . 0.05 dV(max) [mL] . . . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 6.0 t (min) [s] . . . . . . . . 30.0 t (max) [s] . . . . . . . . 90.0 Threshold . . . . . . . . . . . . 300 EQP range . . . . . . . . . . . . yes Limit A [mV,pH..] . . . . . -44.7 Limit B [mV,pH..] . . . . . -244.7 Maximum volume [mL] . . . . . . . 10.0 Termination at slope . . . . . . Yes Slope [mV,pH../mL] . . . . . 50.0 Evaluation prodedure . . . . . . Standard Steepest jump only . . . . . . . Yes Buffer potential 1 . . . . . . . Yes Buffer potential 1 . . . . . 166.4 Buffer potential 2 . . . . . . . Yes Buffer potential 2 . . . . . -144.7Calculation Result name . . . . . . . . . . . . SAN Formula . . . . . . . . . . . . . . R=(QP1+H15)*C/m Constant . . . . . . . . . . . . . . C=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . VP1>0Calculation Result name . . . . . . . . . . . . Acid number Formula . . . . . . . . . . . . . . R2=(QP2+H14)*C2/m Constant . . . . . . . . . . . . . . C2=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . VEQ=0Calculation Result name . . . . . . . . . . . . Acid number Formula . . . . . . . . . . . . . . R3=(Q+H14)*C/m Constant . . . . . . . . . . . . . . C3=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . VEQ]0Rinse Auxiliary reagent . . . . . . . . . Solvent 664 Volume [mL] . . . . . . . . . . . . 20.0

MethodRecord Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes E - V curve . . . . . . . . . . . . Yes Table of measured samples . . . . . Yes dE/dV - V curve . . . . . . . . . . YesConditioning Interval . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . 300 Rinse . . . . . . . . . . . . . Yes Auxiliary reagent . . . . . . . . Solvent 664 Volume [mL] . . . . . . . . . . . 20.0Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . YesConditioning Interval . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . 10

Buffer determination ASTM D 664-89:

Both buffers can be determined automatically with the samplechanger. First buffer A is measured, then buffer B. Theelectrode is conditioned before measuring the next buffer.

Buffer A -> R1 = E[1] = 166.4147 mV -> stored as aux. valueH12Buffer B -> R2 = E[2] = -144.7011 mV -> stored as aux. valueH13

Blank determination for AN Method 059D:Solvent 664-89 is dispensed automatically by a pump.Titrant:KOH in isopropanol, R = Q , stored as aux. value H14

Blank determination for SAN Method 059E:Solvent 664-89 is dispensed automatically by a pump.Titrant:HCl in isopropanol, R = Q , stored as aux. value H15

93

M099

Basic components, expressed as KOH

50 mL solvent mixtureToluene:isopropanol:distilled water(50% (v/v):49.5%(v/v):0.5%(v/v) )

HCl in isopropanol:c(HCl) = 0.1 mol/L

DL50Graphix, DL53/55/58DL70ES, DL77MPC227 conductivity meter

100 mL titration beaker ME-101974Connection cable 513022581 additional burette drive DV90, 1additional DV1010, Printer, balance

METTLER TOLEDO


Preparation and ProceduresMotor oil, 2-4 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

InLab717 conductivity probeIndication

Conductometric Base Number Titration of Motor Oil

1) Titrant preparation:The titrant can be prepared manually by adding 9 mL 37% v/vHCl and filling up to 1 L with isopropanol (2-propanol).

2) The titrant is standardized with a solution of potassiumhydrogen phtalate of known concentration (see applicationM100).

3) MCP227 calibration:3.1 The conductivity meter is calibrated before titration using air(0 µS/cm) and 1413 µS/cm.3.2 The linear output range of the MPC227 conductivity meterhas to be appropriate to the measuring range during thetitration. The range can be set accordingly:a. Press "Read" to stop measuring if necessary. The dor mustnot flash anymore.b. Press "Mode" for 2 seconds. prog appears on the display.c. Keep pressing "Mode" until P5 is reached.d. Select the lowest millivolt output range /midpoint: 20 µS/cm.e. Confirm it by pressing "Mode".e. Return to normal measuring by pressing "Read".f. Check whether you have turned the automatic endpoint off.

4) If the sample contains insoluble material it must be shakenthoroughly in the original container before it is taken.

1) This application is based on the IP400/94 standardpublished by the Institute of Petroleum, London. The followingmodifications to the standard IP method were made:1.1 INC = 0.1 mL at TFIX = 5 s instead of 10 s. The analysis isspeeded up.1.2 Solvent mixture instead of nitric acid is used to rinse theconductivity probe.

2) Most oil samples create sticky residues. The conductivityprobe is cleaned with a paper tissue soaked in solvent mixture.Afterwards, the probe is rinsed again with solvent mixture toremove the last impurities. Therefore, an automatic procedureusing a sample changer is not recommended.

3) If you want to monitor the conductivity values at the titrator,the appropriate slope and unit have to be installed in the sensorsetup of the titrator. For instance, for the selected MPC227range with a midpoint of 20 µS/cm the slope is 9.00 µS/cm,and the unit is µS/cm (Check MPC227 op. instructions p. 17).

Literature: IP 400/94, "Determination of Base Number ofPetroleum Products - Conductimetric titration method"The Institute of Petroleum, London, 1994

Remarks

Base number determination (BN 1):R1 = Q*C/m ; mg KOH/gC1 = M/z

M = 56.1, z =1

Calculation

Determination of the base number in motor oils by conductometric titration according to IP400/94


K. SaegesserAuthor

94


METTLER TOLEDO DL77 Titrator V3.1 Mettler-Toledo GmbH 23 Market Support Laboratory

Method BN 1 BN conductometric 23-Apr-1998 9:50 User K Sägesser Measured 23-Apr-1998 10:23

RESULTS


1/1 Oil 1.009 g Weight m R1 = 10.338 mg KOH/g base number 1/2 Oil 0.961 g Weight m R1 = 0.000 mg KOH/g base number 1/3 Oil 0.974 g Weight m R1 = 10.639 mg KOH/g base number 1/4 Oil 1.023 g Weight m R1 = 10.569 mg KOH/g base number 1/5 Oil 1.0 g Weight m R1 = 10.368 mg KOH/g base number 1/6 Oil 0.974 g Weight m R1 = 10.581 mg KOH/g base number

STATISTICS Number results n = 6 Mean value x = 8.7492 mg KOH/g base number Standard deviation s = 4.2879 mg KOH/g base number Rel. standard deviation srel = 49.01 % Outlier test: sample No. 1/2

Statistics without sample No. 1/2 Number results n = 5 Mean value x = 10.499 mg KOH/g base number Standard deviation s = 0.136165 mg KOH/g base number Rel. standard deviation srel = 1.297 %

Titration curve

Results

95

Method BN 1 BN conductometric Version 23-Apr-1998 9:50

Title Method ID . . . . . . . . . . . . . BN 1 Title . . . . . . . . . . . . . . . BN conductometric Date/time . . . . . . . . . . . . . 23-Apr-1998 9:50Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.5 Upper limit [g] . . . . . . . . . 2.0 ID1 . . . . . . . . . . . . . . . . Oil Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . BN solvent Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 50Stir Speed [m%] . . . . . . . . . . . . . 45 Time [s] . . . . . . . . . . . . . . 120Titration Titrant . . . . . . . . . . . . . . HCl (2-prop) Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . Cond Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing . . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.6 Titrant addition . . . . . . . . INC dV [mL] . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . TFIX dt [s] . . . . . . . . . . . . 5.0 Threshold . . . . . . . . . . . . 50.0 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . SegmentedCalculation Result name . . . . . . . . . . . . base number Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer Sample data . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes

Method

96

M100

KHP

45 mL solvent mixtureToluene:isopropanol:distilled water(50% (v/v):49.5%(v/v):0.5%(v/v) )

HCl in isopropanol:c(HCl) = 0.1 mol/L

DL50Graphix, DL53/55/58DL70ES, DL77MPC227 conductivity meter

100 mL titration beaker ME-101974Connection cable 513022581 additional burette drive DV90, 1additional DV1010, Printer, balance

METTLER TOLEDO


Preparation and Procedures5 mL 0.1 mol/L potassium hydrogenphtalate solution (KHP)

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

InLab717 conductivity probeIndication

Standardization of HCl in Isopropanol by Conductometric Titration

1) Titrant preparation:The titrant can be prepared manually by adding 9 mL 37% v/vHCl and filling up to 1 L with isopropanol (2-propanol).

2) 0.1 mol/L KHP solution:Dissolve KHP in 200 mL water by means of an ultrasonic bathand fill up to 1 L with isopropanol.

3) MCP227 calibration:3.1 The conductivity meter is calibrated before titration using air(0 µS/cm) and 1413 µS/cm.3.2 The linear output range of the MPC227 conductivity meterhas to be appropriate to the measuring range during thetitration. The range can be set accordingly:a. Press "Read" to stop measuring if necessary. The dor mustnot flash anymore.b. Press "Mode" for 2 seconds. prog appears on the display.c. Keep pressing "Mode" until P5 is reached.d. Select the lowest millivolt output range /midpoint: 20 µS/cm.e. Confirm it by pressing "Mode".e. Return to normal measuring by pressing "Read".f. Check whether you have turned the automatic endpoint off.

1) If you want to monitor the conductivity values at the titrator,the appropriate slope and unit have to be installed in the sensorsetup of the titrator. For instance, for the selected MPC227range with a midpoint of 20 µS/cm the slope is 9.00 µS/cm,and the unit is µS/cm (Check MPC227 op. instructions p. 17).

2) MPC227 Linear ranges:

Range 1: 2-200 µS/cmMidpoint: 20 µS/cm; Slope: 9.00 mV/(µS/cm); Unit: µS/cm

Range 2: 20-2000 µS/cmMidpoint: 200 µS/cm Slope: 0.90 mV/(µS/cm), Unit: µS/cm

Range 3: 0.2-20 mS/cmMidpoint: 2.0 mS/cm; Slope: 90.00 mV/(µS/cm); Unit: mS/cm

Range 4: 2-200 mS/cmMidpoint: 20 mS/cm Slope: 9.00 mV/(µS/cm), Unit: mS/cm

Range 5: 20-2000 mS/cmMidpoint: 200 mS/cm Slope: 0.90 mV/(µS/cm), Unit: mS/cm

Remarks

Titer determination (BN 2):R1 = U/(VEQ*c*C)C1 = 1/(0.1*z)

Calculation

Standardization of alcoholic HCl by conductometric titration.

Standard

K. SaegesserAuthor

97


METTLER TOLEDO DL77 Titrator V3.1 Mettler-Toledo GmbH 23 Market Support Laboratory

Method BN 1 BN conductometric 23-Apr-1998 9:50 User K Sägesser Measured 23-Apr-1998 10:23

RESULTS


1/1 Oil 1.009 g Weight m R1 = 10.338 mg KOH/g base number 1/2 Oil 0.961 g Weight m R1 = 0.000 mg KOH/g base number 1/3 Oil 0.974 g Weight m R1 = 10.639 mg KOH/g base number 1/4 Oil 1.023 g Weight m R1 = 10.569 mg KOH/g base number 1/5 Oil 1.0 g Weight m R1 = 10.368 mg KOH/g base number 1/6 Oil 0.974 g Weight m R1 = 10.581 mg KOH/g base number

STATISTICS Number results n = 6 Mean value x = 8.7492 mg KOH/g base number Standard deviation s = 4.2879 mg KOH/g base number Rel. standard deviation srel = 49.01 % Outlier test: sample No. 1/2 Number results n = 5 Mean value x = 10.499 mg KOH/g base number Standard deviation s = 0.136165 mg KOH/g base number Rel. standard deviation srel = 1.297 %

Titration curve

Results

98

Method BN 1 BN conductometric Version 23-Apr-1998 9:50

Title Method ID . . . . . . . . . . . . . BN 1 Title . . . . . . . . . . . . . . . BN conductometric Date/time . . . . . . . . . . . . . 23-Apr-1998 9:50Sample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.5 Upper limit [g] . . . . . . . . . 2.0 ID1 . . . . . . . . . . . . . . . . Oil Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . BN solvent Concentration [mol/L] . . . . . . . 1.0 Volume [mL] . . . . . . . . . . . . 50Stir Speed [m%] . . . . . . . . . . . . . 45 Time [s] . . . . . . . . . . . . . . 120Titration Titrant . . . . . . . . . . . . . . HCl (2-prop) Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . Cond Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing . . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.6 Titrant addition . . . . . . . . INC dV [mL] . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . TFIX dt [s] . . . . . . . . . . . . 5.0 Threshold . . . . . . . . . . . . 50.0 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . SegmentedCalculation Result name . . . . . . . . . . . . base number Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer Sample data . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes

Method

99

M061

Organic acids, lactone, free aminoacids

40 mL deionized water

0.1mol/L HCl; 0.1 mol/L NaOH; 36.5%Formol to pH 8.0 with NaOH

DL70ES/DL77, balance

Free amino acids (formol no.):R-COOH-NH2 + HCHO = H2O + R-COOH-N=CH2

R-COOH-N=CH2 + OH- = R-COO--N=CH2 + H2O

Beakers ME-101974; 2 additionalburette drives DV90; 2 burettesDV1010; 1 Pump ME-51108016 withadapter ME-51108350

METTLER TOLEDO

Aqueous solutionsWastedisposal

Preparation and ProceduresHoney, approx. 10 gSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories


pH, Acidity, Lactone and Formol Value of Honey

1) The sample is weighed in the titration beaker and mounted atthe titration head.

2) Deionized water is automatically added by the peristalticpump.

3) First the pH value and the acidity content are determined.

4) Then the lactone value is determined by means of twotitration.

5) Finally, the formol value is determined after addition of formolsolution which is neutralized to pH 8.

Note:A blank value determination is performed before sampleanalysis. This is used in calculation R3 (Lactone content). Theblank value is stored as auxiliary value H11.

Honey is one of the richest natural products and the oldestsweetener. It contains sugars, water, amino acids, minerals,vitamins, ferments, hormones, inhibitors, other compounds.

1) pH and acidity:Pure blossom honey has generally a pH value of 3.3 - 4.6.The acid content is usually between 7.4 and 30 mmol/kg. If itexceeds 30 mmol/kg , then honey has undergone deteriorationby fermentation/acidification. Organic acids such as tartaric,succinic, citric and oxalic are present in honey. Clover honeymay further contain butyric, acetic, formic and lactic acid.

2) Formol value:The formol value is a measure of the free amino acids. Its usuallevel is between 4.5 and 15.5 mmol/kg. A low formol valueindicates adulteration with artificial honey or additional feedingof the bees with sugar. The formol value is determined byadding a formol solution which must be neutralized priordetermination.

3) Lactone value:The lactone content varies between 2-20 mmol/kg.

Literature:Schweizerisches Lebensmittelbuch, Band II, Chap. 23AOAC Official Methods of Analysis, 1984, pages 595-596

Remarks

pH (R1) & Acidity (R2):R1=E ; R2=Q[1]*C2/m, C2=1000;Lactone content:R3=(Q[2]+Q[3]-H11)*C3,C3=1000/mFormol value:R4=Q[5]*C4/m, C4=1000

Calculation

Method for the determination of the pH, acidity, lactone and formol value of honey.

Standard 1) THAM (NaOH), 2) KHP (HCl)

Ruth von RotzAuthor

100


RESULTS 1/1 Ex.honey 10.3302 g 3.819 pH 21.869 mmol/kg Acidity 15.010 mmol/kg Lactone cont. 8.539 mmol/kg Formol value 1/2 Ex.honey 10.287 g 3.782 pH 21.539 mmol/kg Acidity 14.713 mmol/kg Lactone cont. 8.947 mmol/kg Formol value 1/3 Ex.honey 10.3434 g 3.768 pH 21.689 mmol/kg Acidity 14.879 mmol/kg Lactone cont. 8.982 mmol/kg Formol value 1/4 Ex.honey 10.3955 g 3.766 pH 21.536 mmol/kg Acidity 14.981 mmol/kg Lactone cont. 9.095 mmol/kg Formol value 1/5 Ex.honey 10.3756 g 3.764 pH 21.577 mmol/kg Acidity 14.683 mmol/kg Lactone cont. 9.079 mmol/kg Formol value

STATISTICS Number results R2 n = 5 Mean value x = 21.642 mmol/kg Acidity Standard deviation s = 0.1413 mmol/kg Acidity Rel. standard deviation srel = 0.653 % Outlier test: no outliers!STATISTICS Number results R3 n = 5 Mean value x = 14.853 mmol/kg Lactone cont. Standard deviation s = 0.1504 mmol/kg Lactone cont. Rel. standard deviation srel = 1.013 % Outlier test: no outliers!STATISTICS Number results R4 n = 5 Mean value x = 21.642 mmol/kg Formol value Standard deviation s = 0.1413 mmol/kg Formol value Rel. standard deviation srel = 0.653 % Outlier test: Sample No. 1/1

Statistics without sample No 1/1 Number results R4 n = 4 Mean value x = 9.026 mmol/kg Formol value Standard deviation s = 0.0723 mmol/kg Formol value Rel. standard deviation srel = 0.801 % Outlier test: no outliers!

pH Acidity Lactone Formol valueSample Result RSD Result RSD Result RSD Result RSD (%) (mmol/kg) (%) (mmol/kg) (%) mmol/kg) (%)Mountain honey 3.78 0.61 21.64 0.65 14.85 1.01 8.93 2.54French honey 4.01 0.33 17.11 0.70 10.16 1.65 4.27 1.95Swiss honey 1 4.37 0.33 11.59 0.75 6.39 2.57 2.36 3.56Swiss honey 2 3.98 0.69 8.51 0.81 3.95 4.85 2.77 0.30

Titration curve

Results

101

Method R1 pH,ac.,lact.,form. No Honey Version 11-July-1991 1:23 pm

Title Method ID . . . . . . . . . . . . . R1 Title . . . . . . . . . . . . . . . pH,ac.,lact.,form. No Honey Date/time . . . . . . . . . . . . . 11-July-1991 1:23 pmSample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 9.0 Upper limit [g] . . . . . . . . . 11.0 ID1 . . . . . . . . . . . . . . . . CH honey Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1Pump Auxiliary reagent . . . . . . . . . H2O Volume [mL] . . . . . . . . . . . . 40.0Stir Speed [%] . . . . . . . . . . . . . 90 Time [s] . . . . . . . . . . . . . . 150Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 30Measure Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.5 t(min) mode . . . . . . . . . Fix t (min) [s] . . . . . . . . 10.0 t (max) [s] . . . . . . . . 30.0Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . 0.7 Titrant addition . . . . . . . . Dynamic dV (set)[mV] . . . . . . . 8.0 dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.1 dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 0.5 t (min) [s] . . . . . . . . 2.0 t (max) [s] . . . . . . . . 20.0 End point mode . . . . . . . . . EPA Potential [mV,pH..] . . . . 7.0 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 10.0Record Output unit . . . . . . . . . . . . Printer Table of measured values . . . . . . YesTitration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . 3.0 Titrant addition . . . . . . . . Dynamic dV (set)[mV] . . . . . . . 8.0 dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.3 dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 0.5 t (min) [s] . . . . . . . . 2.0 t (max) [s] . . . . . . . . 20.0 End point mode . . . . . . . . . EPA Potential [mV,pH..] . . . . 9.8 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 60Dispense Titrant . . . . . . . . . . . . . . HC1 Concentration [mol/L] . . . . . . . 0.1 Volume [mL] . . . . . . . . . . . . 5.0Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Titrant addition . . . . . . . . Continuous Control band[mV,pH..] . . . . 3.0 Delay [s] . . . . . . . . . . 10 End point mode . . . . . . . . . EPA Potential [mV,pH..] . . . . 7.0 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 10.0Record Output unit . . . . . . . . . . . . Printer Table of measured values . . . . . . YesTitration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Titrant addition . . . . . . . . Continuous Control band[mV,pH..] . . . . 2.0 Delay [s] . . . . . . . . . . 10 End point mode . . . . . . . . . EPA Potential [mV,pH..] . . . . 8.0 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 10.0

MethodDispense Titrant . . . . . . . . . . . . . . Formol 36.5% Concentration [mol/L] . . . . . . . 36.5 Volume [mL] . . . . . . . . . . . . 15.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 60Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Titrant addition . . . . . . . . Continuous Control band[mV,pH..] . . . . 3.0 Delay [s] . . . . . . . . . . 10 End point mode . . . . . . . . . EPA Potential [mV,pH..] . . . . 8.0 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 10.0Calculation Result name . . . . . . . . . . . . pH Formula . . . . . . . . . . . . . . R=E Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . Acidity Formula . . . . . . . . . . . . . . R2=Q[1]*C2/m Constant . . . . . . . . . . . . . . C2=1000 Result unit . . . . . . . . . . . . mmol/kg Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . Lactone cont. Formula . . . . . . . . . . . . . . R3=(Q[2]+Q[3]-H11)*C3 Constant . . . . . . . . . . . . . . C3=1000/m Result unit . . . . . . . . . . . . mmol/kg Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . Formol value Formula . . . . . . . . . . . . . . R4=Q[5]*C4/m Constant . . . . . . . . . . . . . . C4=1000 Result unit . . . . . . . . . . . . mmol/kg Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Raw results last sample . . . . . . Yes Results last sample . . . . . . . . Yes Table of measured values . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R4 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Method R1a Blank for Honey Version 11-07-1991 11:25 am

Title Method ID . . . . . . . . . . . . . R1a Title . . . . . . . . . . . . . . . Blank for Honey Date/time . . . . . . . . . . . . . 11-07-1991 11:25 amSample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 5.0 ID1 . . . . . . . . . . . . . . . . Blank Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 30Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . 3.0 Titrant addition . . . . . . . . Dynamic dV (set)[mV] . . . . . . . 8.0 dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.2 dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 0.5 t (min) [s] . . . . . . . . 2.0 t (max) [s] . . . . . . . . 20.0 End point mode . . . . . . . . . EPA Potential [mV,pH..] . . . . 7.0 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 10.0Calculation Result name . . . . . . . . . . . . Formula . . . . . . . . . . . . . . R=Q[1] Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Table of measured values . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesAuxiliary value

ID t t Bl k l t

102

M240

Organic acids, free amino acids

50 mL deionized water

NaOH, c(NaOH) = 0.5 mol/LFormol , c(Formol) = 36.5%Adjusted to pH 8.2 with NaOH

DL70ES/DL77Rondo 60 sample changerBalance, printer

Free amino acids (formol no.):R-COOH-NH2 + HCHO = H2O + R-COOH-N=CH2

R-COOH-N=CH2 + OH- = R-COO--N=CH2 + H2O

Beakers ME-101974;1 additional burette drive DV90;1 burette DV1010;1 additional diaphragma pump (DOSE)

METTLER TOLEDO

Aqueous solutionWastedisposal

Preparation and ProceduresConcentarted orange juice, 1-4 g Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories


Formol Number, Acidity and True Brix Value of Orange Juice

1) The DG111 electrode must be calibrated with pH buffers.

2) The sample is weighed in the titration beaker and mounted atthe titration head. If drinkable orange juice is used, then weighin approximately 20 g. The sample is diluted using the secondpump of the sample changer (DOSE).

3) First the acidity content is determined by performing an EPtitration to pH 8.2 with NaOH. This is given as citric acidcontent.

4) Formol is dispensed by the second burette. After 1 minutereaction time, an EP titration to pH 8.2 with NaOH is started.

5) The formol number is defined in calculation R4 as mmolNaOH/10g sample, normalized to 65 True Brix:FN = (mmol NaOH*10*10*65)/(m*True Brix).

6) A blank is run and stored as auxiliary value H2.

Note:1. The molar mass M is set to 1.0 and is not used.2. Prior titration the Brix value of the sample is measured with arefractometer. The value is stored as auxiliary value H1and usdin calculation R3 (correction for true brix).

1) Formol value:The formol value is a measure of the free amino acids andallows an estimation of of the protein content.Amino acids can not be titrated directly with a base since thedissociation constant of the -COOH group is too weak. Byadding formaldehyde, the amino group -NH2 of the amino acidsreacts forming to -N=CH2 . As a consequence, the dissociationstrength of the hydrogen atom present in the carboxylic group-COOH of the amino acid i increased. The amino acid can bedirectly titrated with sodium hydroxide.

2) The formol value is generally given as the titrantconsumption of 0.1 mol/L NaOH needed for 10 g or sample.

3) True Brix: correction of the measured refrative index for thecitric acid concentration (given in R1):Corrected value = (-0.00035)*R12 + 0.191*R1 + 0.024(According to Stevens and Baier, 1959)

Literature:NEN 2843, NEN 2861J. Stevens, W.Baier, Die Fruchtsaftindustrie, 4 (1959), p. 28.(See also: C.W. Lindsay, J. of AOAC International,Vol. 76, NO.2, 1993, page 424).AOAC Official Methods of Analysis, 1984.

Remarks

Citric acid (R1):R1 = Q[1]*C1/m, C1= 192/(10*3);True Brix correction (R2):R2 = R1*R1*(-0.000035)+C2,C2 = (R1*0.191)+0.024True Brix (R3): R3 = H1+R2Formol No. R4 = 6500*C4/(m*R3),C4=Q[2]-H2+QEX[1]

Calculation

Method for the determination of the formol number, acidity and true Brix value of orange juice according toNEN 2843 and NEN 2861 (Dutch standards).

Standard THAM (NaOH)

Ko Schaap, MT-NLAuthor

103


METTLER DL70 Titrator Quest Naarden Analytical Laboratory

4 F.N./Acid./True Brix measured 30-Oct-1991 11:1311-Oct-1991 9:00 TitratorSW Version 2.0 User jan

RESULTS

No Identification Weight Results

1/1 11570 03500 1.5503 g 31.3 % Citric acid 5.66 True Bx corr. 57.76 True brix 18.35 mmol NaOH/10g(65wBx) 1/2 11570 03500 1.5503 g 31.4 % Citric acid 5.67 True Bx corr. 57.77 True brix 18.35 mmol NaOH/10g(65wBx)

STATISTICS Number results R1 n = 2 Mean value x = 31.3 % Citric acid Standard deviation s = 0.04 % Citric acid Rel. standard deviation srel = 0.138 %

STATISTICS Number results R2 n = 2 Mean value x = 5.67 True Bx. corr. Standard deviation s = 0.1504 True Bx. corr. Rel. standard deviation srel = 1.013 %

STATISTICS Number results R3 n = 2 Mean value x = 57.77 True brix Standard deviation s = 0.007 True brix Rel. standard deviation srel = 0.013 %

STATISTICS Number results R4 n = 2 Mean value x = 18.66 mmol NaOH/10g(65wBx) Standard deviation s = 0.443 mmol NaOH/10g(65wBx) Rel. standard deviation srel = 2.374 % Outlier test: no outliers!

Titration curve

Results

104

Method 4 F.N./Acid./True Brix Version 11-Oct-1991 9:00

Title Method ID . . . . . . . . . . . . . R1 Title . . . . . . . . . . . . . . . F.N./Acid./True Brix Date/time . . . . . . . . . . . . . 11-Oct-1991 9:00Conditioning Interval . . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . . 10Sample Number samples . . . . . . . . . . . 2 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 1.0 Upper limit [g] . . . . . . . . . 4.0 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 1.0 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 70 Time [s] . . . . . . . . . . . . . . 15Auxiliary instrument Name . . . . . . . . . . . . . . . . DOSE Time [s] . . . . . . . . . . . . . . 5.0Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.5 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Titrant addition . . . . . . . . Dynamic dE(set)[mV] . . . . . . . . . 4.0 dV(min) [mL] . . . . . . . . . 0.005 dV(max) [mL] . . . . . . . . . 0.5 dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 0.5 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 20.0 End point mode . . . . . . . . . EPA Potential [mV,pH..] . . . . 8.2 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 30.0Dispense Titrant . . . . . . . . . . . . . . Formol Concentration [mol/L] . . . . . . . 36.5% Volume . . . . . . . . . . . . . . 10 mLStir Speed [%] . . . . . . . . . . . . . 70 Time [s] . . . . . . . . . . . . . . 60Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.5 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Titrant addition . . . . . . . . Continuous Control band [mV,pH,...] . . 3.0 Delay [s] . . . . . . . . . . 10 End point mode . . . . . . . . . EPA Potential [mV,pH..] . . . . 8.2 Tendency . . . . . . . . . . . . Positive Maximum volume [mL] . . . . . . . 20.0Rinse Auxiliary reagent . . . . . . . . . H2O Volume [mL] . . . . . . . . . . . . 10.0Conditioning Interval . . . . . . . . . . . . . . 1 Time [s] . . . . . . . . . . . . . . 10Calculation Result name . . . . . . . . . . . . Citric acid Formula . . . . . . . . . . . . . . R1=Q[1]*C1/m Constant . . . . . . . . . . . . . . C1=192/(m*3) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 1Calculation Result name . . . . . . . . . . . . True Bx corr. Formula . . . . . . . . . . . . . . R2=R1*R1*(-0.00035)+C2 Constant . . . . . . . . . . . . . . C2=(R1*0.191)+0.024 Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2

MethodCalculation Result name . . . . . . . . . . . . True brix Formula . . . . . . . . . . . . . . R3=H1+R2 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2Calculation Result name . . . . . . . . . . . . mmol NaOH/10g(65wBx) Formula . . . . . . . . . . . . . . R4=6500*C4/(m*R3) Constant . . . . . . . . . . . . . . C4=Q[2]-H2+QEX[1] Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R4 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

105

M241 / 1

ITRB, accessible surface area:83.0 x103 m2/kg

45 mL deionized water5 mL 0.15% Triton X-10010 mL 0.01 mol/L CTAB(Cetyltrimethylammonium bromide)

Dioctyl sodium sulfosuccinate(Aerosol OT)c(Aerosol OT) = 0.1 mol/L

DL70ES, DL77Rondo 60 sample changerAT261 Balance, printer

2 additional burette drive DV90,2 additional burette DV1010100 mL titration beaker ME-101974DT120 Temperature sensor

METTLER TOLEDO

Aqueous wasteWastedisposal

Preparation and Procedures5 Standard samples with ITRB5 samples (0.2-0.6 g, with 0.1 g diff.)ITRB (Industry Tint Reference Black)

Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DP550 with adapter cable ME-89600Indication

Carbon Black Surface Area (ASTM D3765-99): Standardization

The sample must be prepared according to ASTM D3765-99.After filtration, the standard samples are ready for titration:

1) Add 45 mL deionized water2) Mount the beaker on the titration stand, start method ALG1.3) 5 mL 0.15% Triton X-100 solution are added by a burette,4) 10 mL 0.01 CTAB solution are added by a second burette.

CTAB Standard solution (0.01 mol/L):Dissolve 3.64 g of reagent-grade CTAB (Cetyltrimethylammonimbromide, available from e.g. J.T. Baker, Cat. No. 7N121) in900 mL distilled or deionized water. Add 100 mL of the pH 7.00.05 mol/L buffer solution. Warm the solution to a temperatureof 27-37°C to facilitate the dissolution. Cool to a temperaturebetween 22 and 25°C before using.

Aerosol OT (Dioctyl sodium sulfosuccinate):Dissolve 1g/L of Aerosol OT solution in distilled or deionizedwater containing 2.5 mL/L of 37% formaldehyde, by swirlingvogourously with a magnetic stirrer for 48 h. Allow to stand anadditional twelve days before standardization and use. Thesolution should be capped tightly and stored in a cool place(once opened, the solution should be store in a dessiccator).

This method covers the measurement of the specific surfacearea of carbon black exclusive of area contained in microporestoo small to admit CTAB molecules. This test method is suitablefor characterizing rubber-grade carbon blacks of all types.

The CTAB adsorption by carbon black is independent of residualtars and functional groups containing hydrogen and oxygen, etc.Rapid equilibration is achieved by mechanical stirring andultrasonic vibration. The CTAB molecule is relatively large; so itis not adsorped in micropores or on surface roughness. Thus,the CTAB surface area reflects only the surface f the carbon blackthat is available for interaction with rubber molecules.

Titration with Aerosol OT solution to a turbidity maximumendpoint is used to determine the unadsorped CTAB afterremoval of the colloidally dispersed carbon black byultrafiltration.

All results are scaled by using the Industry Tint reference Black(ITRB) as a primary standard and taking its accessible surfacearea to be exactly 83.0 x 103 m2/kg.

Literature:ASTM D3765 (www.astm.org)

Remarks

See method belowCalculation

Titration of unadsorbed CTAB (cetyltrimethylammonium bromide) on the ITRB standards for the carbonblack surface area determination according to ASTM D3765-99 (see also 241 / 2, and 241 / 3).

Standard ---

K. Mooibroek/C. Gordon/Ch. WalterAuthor

106

Table of measured values Titration curve

Results

107

Method ALG1 ASTM3765: Standards Version 22-Feb-2002 10:30

Title Method ID . . . . . . . . . . . . . ALG1 Title . . . . . . . . . . . . . . . ASTM3765: Standards Date/time . . . . . . . . . . . . . 22-Feb-2002 10:30Sample Number samples . . . . . . . . . . . 5 Titration stand . . . . . . . . . . ST20 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.2 Upper limit [g] . . . . . . . . . 0.6 ID1 . . . . . . . . . . . . . . . . ITRB Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . TEMP ADispense Titrant . . . . . . . . . . . . . . Triton X-100 Concentration [mol/L] . . . . . . . 0.15 Volume [mL] . . . . . . . . . . . . 5.0Dispense Titrant . . . . . . . . . . . . . . CTAB Concentration [mol/L] . . . . . . . 0.01 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 30Titration Titrant . . . . . . . . . . . . . . Aerosol OT Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . INC dV[mL] . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 500 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure. . . . . . . MinimumCalculation Result name . . . . . . . . . . . . Volume/gram Formula . . . . . . . . . . . . . . R1=VEQ/m Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . cm3/g Decimal places . . . . . . . . . . . 4Auxiliary value ID text . . . . . . . . . . . . . . H20 1. standard Formula . . . . . . . . . . . . . . H20=mAuxiliary value ID text . . . . . . . . . . . . . . ITBR(1) Formula . . . . . . . . . . . . . . H1=R1 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . f=1Auxiliary value ID text . . . . . . . . . . . . . . H19 2. standard Formula . . . . . . . . . . . . . . H19=mAuxiliary value ID text . . . . . . . . . . . . . . ITBR(2) Formula . . . . . . . . . . . . . . H2=R1 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . f=2Auxiliary value ID text . . . . . . . . . . . . . . H18 3. standard Formula . . . . . . . . . . . . . . H18=mAuxiliary value ID text . . . . . . . . . . . . . . ITBR(3) Formula . . . . . . . . . . . . . . H3=R1 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . f=3

MethodAuxiliary value ID text . . . . . . . . . . . . . . H17 4. standard Formula . . . . . . . . . . . . . . H17=mAuxiliary value ID text . . . . . . . . . . . . . . ITBR(4) Formula . . . . . . . . . . . . . . H4=R1 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . f=4Auxiliary value ID text . . . . . . . . . . . . . . H16 5. standard Formula . . . . . . . . . . . . . . H16=mAuxiliary value ID text . . . . . . . . . . . . . . ITBR(5) Formula . . . . . . . . . . . . . . H5=R1 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . f=5Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

108

M241 / 2






METTLER TOLEDO



Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories


Carbon Black Surface Area (ASTM D3765-99): Linear regression

For the calculation of the calibration line starts method ALG2.




The CTAB adsorption by carbonn black is independent ofresidual tars and functional groups containing hydrogen andoxygen, etc. Rapid equilibration is achieved by mechanicalstirring and ultrasonic vibration. The CTAB molecule is relativelylarge; so it is not adsorped in micropores or on surfaceroughness. Thus, the CTAB surface area reflects only the surfacef the carbon black that is available for interaction with rubbermolecules.

Titration with Aerosol OT soltuion to a turbidity maximumendpoint is used to determine the unadsorped CTAB afterremoval of the colloidally dispersed carbon black byultrafiltration.



Remarks

Calculation of linear regression:see below

Calculation

Linear regression for calibration line of Carbon Black Area Determination according to ASTM D3765-99.Five ITRB standards have been determined in Application 241/1, while sample titration is described in 241/3.

Standard ---


109


Results

110

Method ALG2 ASTM3765: Lin. regr. Version 22-Feb-2002 11:30

Title Method ID . . . . . . . . . . . . . ALG2 Title . . . . . . . . . . . . . . . ASTM3765: Lin. regr. Date/time . . . . . . . . . . . . . 22-Feb-2002 11:30Sample Number samples . . . . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mol/L] . . . . . . . . . 1.0 ID1 . . . . . . . . . . . . . . . . ITRB Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . TEMP AAuxiliary value ID text . . . . . . . . . . . . . . Sum of masses (1) Formula . . . . . . . . . . . . . . H6=H20+H19+H18Auxiliary value ID text . . . . . . . . . . . . . . Sum of masses (2) Formula . . . . . . . . . . . . . . H7=H6+H17+H16Auxiliary value ID text . . . . . . . . . . . . . . Sum of volumes Formula . . . . . . . . . . . . . . H8=H1+H2+H3+H4+H5Auxiliary value ID text . . . . . . . . . . . . . . Products (1) Formula . . . . . . . . . . . . . . H9=H20*H1+H19*H2Auxiliary value ID text . . . . . . . . . . . . . . Products (2) Formula . . . . . . . . . . . . . . H10=H18*H3+H17*H4Auxiliary value ID text . . . . . . . . . . . . . . Products (3) Formula . . . . . . . . . . . . . . H11=H16*H5Auxiliary value ID text . . . . . . . . . . . . . . Sum of products Formula . . . . . . . . . . . . . . H12=H9+H10+H11Auxiliary value ID text . . . . . . . . . . . . . . Sum of squares (1) Formula . . . . . . . . . . . . . . H13=sq(H20)+sq(H19)Auxiliary value ID text . . . . . . . . . . . . . . Sum of squares (2) Formula . . . . . . . . . . . . . . H14=sq(H18)+sq(H17)Auxiliary value ID text . . . . . . . . . . . . . . Sum of squares (3) Formula . . . . . . . . . . . . . . H15=H13+H14+sq(H16)Calculation Result name . . . . . . . . . . . . Top line calc. (1) Formula . . . . . . . . . . . . . . R1=4*H12 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Top line calc. (2) Formula . . . . . . . . . . . . . . R2=-H7*H8 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Top line calc. (3) Formula . . . . . . . . . . . . . . R3=R1+R2 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4

MethodCalculation Result name . . . . . . . . . . . . Bottom line calc. (1) Formula . . . . . . . . . . . . . . R4=-sq(H7) Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Bottom line calc. (2) Formula . . . . . . . . . . . . . . R5=4*H15 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Bottom line calc. (3) Formula . . . . . . . . . . . . . . R6=R4+R5 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Slope b Formula . . . . . . . . . . . . . . R7=R3/R6 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . cm3/g Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Intercept, V0 (1) Formula . . . . . . . . . . . . . . R8=H8/4 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . cm3

Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Intercept, V0(2) Formula . . . . . . . . . . . . . . R9=(R7*H7)/4 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . cm3

Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Intercept, V0 (3) Formula . . . . . . . . . . . . . . R10=R8-R9 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . cm3

Decimal places . . . . . . . . . . . 4Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

111

M241 / 3






METTLER TOLEDO



Sample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories


Carbon Black Surface Area (ASTM D3765-99): Sample Titration

The sample must be prepared according to ASTM D3765-99.1) Dry an adequate sample of carbon black at 125°C for 1 hourand cool in dessiccator.2) Weigh to 0.1 mg a suitable sample into a glass vial, andproceed according to ASTM D3765-99, chap. 9.After filtration, the samples are ready for titration:1) Add 45 mL deionized water2) Mount the beaker on the titration stand, start method ALG3.3) 5 mL 0.15% Triton X-100 solution are added by a burette,4) 10 mL 0.01 CTAB solution are added by a second burette.




The CTAB adsorption by carbonn black is independent ofresidual tars and functional groups containing hydrogen andoxygen, etc. Rapid equilibration is achieved by mechanicalstirring and ultrasonic vibration. The CTAB molecule is relativelylarge; so it is not adsorped in micropores or on surfaceroughness. Thus, the CTAB surface area reflects only the surfacef the carbon black that is available for interaction with rubbermolecules.

Titration with Aerosol OT soltuion to a turbidity maximumendpoint is used to determine the unadsorped CTAB afterremoval of the colloidally dispersed carbon black byultrafiltration.



Remarks

Calculation

Sample titraiton according to Carbon Black Area Determination according to ASTM D3765-99.Five ITRB standards have been determined in Application 241/1, the calibration line is described in 241 / 2 .

Standard ---


112


Results

113

Method ALG3 ASTM3765: Sample det. Version 24-Jan-1995 11:13

Title Method ID . . . . . . . . . . . . . AL3 Title . . . . . . . . . . . . . . . ASTM3765: Sample det. Date/time . . . . . . . . . . . . . 24-Jan-1995 11:13Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.15 Upper limit [g] . . . . . . . . . 0.25 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 100.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . TEMP AStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . Aerosol OT Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . INC dV[mL] . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 500.0 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure. . . . . . . Minimum Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Result name . . . . . . . . . . . . Consumption Formula . . . . . . . . . . . . . . R=VEQ Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mL Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Result last sample . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Method

114

M242

Basic components

60 mL glacial acetic acid

Perchloric acid in glacial acetic acid:c(HClO4) = 0.1 mol/L


100 mL glass titration beakerME-101446, DV1010 burette, printer,balance

METTLER TOLEDO


Preparation and ProceduresMOCA, PPG, FCA-504 polymersSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SCIndication

Determination of Amine Number

1) The sample mass depends on the amine number.

2) Recommended titrant consumption: 5-10 mL

Electrode cleaning:1) Rinse the electrode after each titration withacetone

2) Soak it in water for at least 2 minutes to allow hydratation ofthe pH sensitive membrane glass.

3) Rinse again with acetone or glacial acetic acid before nexttitration.

The amine value is the amount of substance of perchloric acidused for sample titration. It is expressed as mg KOH / g sample.

If necessary , perform a blank value titration of the solvent.

Literature:Application DL40RC No. 84-05.

Remarks

Blank determination (Meth. blv):R1 = QR1 is stored as auxiliary value H5


Calculation

Determination of the acid number in several polymers by titration with perchloric acid.

Standard THAM, 50-100 mg

MSGAuthor

115


DL40RC:

*** 17-FEB-84 ***

METHOD 8405 2114IDENT. 530SAMPLE NO. 3

*R * MG/G 198.71

Results:

Sample Weight Result St.Dev. n in g mg KOH/g in %

MOCA ca. 0.1 415.58 0.11 2

ML-530 ca. 0.2 200.32 0.80 3

FCA-504 ca. 0.3 143.79 0.71 2

Statistics:n 3Mean: 200.32Stand. dev% .80

Titration curve

Results

116

Method 40016 Amine number det. Version 25-Mar-2002 10:00

Title Method ID . . . . . . . . . . . . . 40016 Title . . . . . . . . . . . . . . . Amine number det. Date/time . . . . . . . . . . . . . 25-Mar-2002 10:00Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 120EQP Titration Titrant . . . . . . . . . . . . . . HClO4

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . Yes Volume [mL] . . . . . . . . . . . 5.0 Titrant addition . . . . . . . . . . INC dV [mL] . . . . . . . . . . . . . 0.25 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 40 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination Maximum volume [mL] . . . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . ml Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R2=(Q-H5)*C2/m Constant . . . . . . . . . . . . . . C2=M/z Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mg KOH/g Result name . . . . . . . . . . . . Amine Number Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Report Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

MethodMethod bv Blank value Version 25-Mar-2002 10:30

Title Method ID . . . . . . . . . . . . . bl Title . . . . . . . . . . . . . . . Blank value Date/time . . . . . . . . . . . . . 25-Mar-2002 10:30Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Volume Volume [mL] . . . . . . . . . . . 60.0 Molar mass M . . . . . . . . . . . . 56.1 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 120EQP Titration Titrant . . . . . . . . . . . . . . HClO4

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.3 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 40 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination Maximum volume [mL] . . . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Auxiliary value ID text . . . . . . . . . . . . . . Blindwert Formula . . . . . . . . . . . . . . H5=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of values . . . . . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

117

M243

OCl- and HOCl

KH2PO4 (Merck pro analysi, 136.09 g*mol-1)Na2HPO4*12 H2O (Merck pro analysi, 358.14 g*mol-1)KI (Fluka puriss, 166.01 g*mol-1); KIO3 (Fluka puriss, 214 g*mol-1)NaOH (Merck Titrisol, 1 M); Acedic acid (Fluka puriss, 60.05 g*mol-1)Phenylarsine Oxide (Sigma, min. 97%, 168.0 g*mol-1)CHCl3 (Fluka purum, 119.38 g*mol-1); HCl (Merck Titrisol, 1 M)

0.00282 M Phenylarsine Oxide (PAO)(= 0.00564 N PAO)

DL5xRondo 60 with diaphragm pump

Titer:KIO3 + 5 KI + 6H+ --> 3 I2 + 6 K+ + 3 H2OC6H5AsIIIO + I2 + 2 H2O --> C6H7AsVO3 + 2 HI

Sample:Cl2 in waste water --> HOCl, OCl-, Cl-, ClNR2, ...C6H5AsIIIO + OCl- (HOCl) + H2O --> C6H7AsVO3 + Cl- (HCl)

KF Option Card ME-51 107 269250 mL Titration beakers ME-23829Printer

METTLER TOLEDO

Collect all arsine containinig solutionsin a separate, designated tank

Wastedisposal

Preparation and ProceduresChlorine treated waste waterSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM 143Indication

Free available chlorine residual in water according to ASTM D 1253 - 86

1) 250 mL 0.4 M phosphate buffer pH 7.0:Weight in 6.35 g KH2PO4 and 21.5 g Na2HPO4 * 12 H2O and fill up to 250 mL withdest. water.

2) 250 mL 0.3 M KI:Weight in 12.5 g KI and fill up to 250 mL with dest. water.

3) 150 mL 0.3 M NaOH:Take 45 mL 1 M NaOH and add 105 mL of dest. water.

4) 100 mL 0.1 M HCl:Take 10 mL 1 M HCl and fill up to 100 mL with dest. water.

5) 1L 0.0047 M KIO 3:Weight in 1.0058 g KIO3 and fill up to 1L with dest. water.

6) 1L 0.00282 M Phenylarsine Oxide (PAO):Weight in 0.8 g PAO and add 150 mL 0.3 M NaOH. Even upon fast stirring not allthe PAO will dissolve. After settling, transfer 110 mL of the saturated solution into a1L measuring cylinder, add 800 mL dest. water and adjust the pH between 6 and7 using 0.1 M HCl. Fill up to 1L with dest. water and add 1 mL of CHCl 3 forpreservation.Standardize the resulting solution to 0.00282 M (0.00564 N) against 0.0047 M(0.0282 N) KIO3 in the following way:Take 0.5 mL 0.0047 M KIO3, add 150 mL dest. water, 5 mL 0.3 M KI and (shortlybefore the titration) 1 pipette of concentrated acedic acid. Titrate this sample withthe prepared PAO-solution using the titer-determination-method described in themethod section.

7) Sample preparation:Take 200 mL sample and add 1 mL 0.4 M phosphate buffer pH 7.0.

The method is reliable down to a Cl2-concentration of about 100ppb.Below this concentration the relative standard deviation (rsd) ofa sample series increases dramatically.However, the method is well suitable to (qualitatively) detecttraces of free available chlorine in waste water.

Measured sample series:

2 ppm Cl2: rsd = 0.082 % (3 samples)500 ppb Cl2: rsd = 7.402 % (3 samples, see results)100 ppb Cl2: rsd = 3.442 % (4 samples)50 ppb Cl2: rsd = 31.242 % (3 samples)

Method adjustment for different Cl2-Concentrations:

Titrant addition Termination dV [mL] at maximum volume [mL]

2 ppm Cl2: 0.3 3.0500 ppb Cl2: 0.06 1.2 (see method)100 ppb Cl2: 0.012 0.250 ppb Cl2: 0.006 0.1

Remarks

free available chlorine - conc. in mmol / LR1 = Q * C1 / m; C1 = 1000 / z

free available chlorine - conc. in mg / LR2 = Q * C2 / m; C2 = 1000 * M / z

Calculation

Determination of free available chlorine residual (residual consisting of hypochlorite ions (OCl-),hypochlorous acid (HOCl) or combination thereof) in chlorine treated water by direct amperometric titration

Standard 0.0047 M KIO3 (= 0.0282 N KIO3)

Mike TreyerAuthor

118


Method 3333 Titer 0.00564 N PAO 31-May-2002 12:50 pmMeasured 31-May-2002 1:07 pmUser Mike Treyer

ALL RESULTSNo. ID Sample size and results

1 KIO3 0.5 mL R1 = 1.21625 Titer2 KIO3 0.5 mL R1 = 1.21086 Titer3 KIO3 0.5 mL R1 = 1.21383 Titer4 KIO3 0.5 mL R1 = 1.21313 Titer

STATISTICSNumber of results R1 n = 4Mean value x = 1.21352 TiterStandard deviation s = 0.00222 TiterRel. standard deviation srel = 0.183 %TITERTitrant PAO 0.00564 mol/LNew titer t = 1.21352

Method 3341 free available chlorine residual 06-Jun-2002 2:50 pmMeasured 06-Jun-2002 3:20 pmUser Mike Treyer

ALL RESULTSNo. ID Sample size and results

1 Waste water 200.0 mL R1 = 0.007 mmol/L Cl2-Concentration R2 = 0.521 mg/L Cl2-Concentration2 Waste water 200.0 mL R1 = 0.008 mmol/L Cl2-Concentration R2 = 0.585 mg/L Cl2-Concentration3 Waste water 200.0 mL R1 = 0.007 mmol/L Cl2-Concentration R2 = 0.512 mg/L Cl2-Concentration

STATISTICSNumber of results R1 n = 3Mean value x = 0.008 mmol/L Cl2-ConcentrationStandard deviation s = 0.00056 mmol/L Cl2-ConcentrationRel. standard deviation srel = 7.407 %Number of results R2 n = 3Mean value x = 0.540 mg/L Cl2-ConcentrationStandard deviation s = 0.03997 mg/L Cl2-ConcentrationRel. standard deviation srel = 7.407 %

Titration curve

Results

119

Method 3333 Titer 0.00564 N PAO Version 31-May-2002 12:50 pm

Title Method ID . . . . . . . . . . . .3333 Title . . . . . . . . . . . . . Titer 0.00564 N PAO Date/time . . . . . . . . . . . .31-May-2002 12:50Sample Sample ID . . . . . . . . . . . . KIO3

Entry type . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . .0.5 Molar mass M . . . . . . . . . . . 214.00 Equivalent number z . . . . . . . 6 Titration stand . . . . . . . . . ST20A Pump . . . . . . . . . . . . . No Pump . . . . . . . . . . . . . No Rinse . . . . . . . . . . . . .Yes Solvent . . . . . . . . . .H2O Volume[mL] . . . . . . . . 20.0 Conditioning . . . . . . . . . No Temperatur sensor . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . 30EQP Titration (Ipol/Upol) Titrant/Sensor Titrant . . . . . . . . . . . .PAO Concentration [mol/L] . . . . 0.00564 Sensor . . . . . . . . . . . . DM143 Indication . . . . . . . . . . . . Amperometric Upol [mV] . . . . . . . . . . .500.0 Predispensing . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . 1.5 Wail time [s] . . . . . . . . . 20 Titrant addition dV [mL] . . . . . . . . . . . . 0.05 Measure mode . . . . . . . . . . . Equilibrium controlled dE [mV, µA] . . . . . . . . . . 0.2 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . 5.0 Steepest jump only . . . . . . .No Range . . . . . . . . . . . . . .No Tendency . . . . . . . . . . . .None Termination at maximum volume [mL] . . . . . 5.0 at potential . . . . . . . . . .No at slope . . . . . . . . . . . .No after number EQPs . . . . . . . .Yes n = . . . . . . . . . . . . 1 comb. termination conditions . .No Evaluation Procedure . . . . . . . . . . . .Minimum Potential 1 . . . . . . . . . . .No Potential 2 . . . . . . . . . . .No Stop for reevaluation . . . . . .Yes Condition . . . . . . . . . .neq=0Calculation Formula . . . . . . . . . . . . . .R1=m/(VEQ*c*C1) Constant . . . . . . . . . . . . . .C1=1/(H1*z) {H1 = 0.0047 M = Conc. of standard KIO3-solution}

Decimal places . . . . . . . . . . .5 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . .Titer Statistics . . . . . . . . . . . . .YesTiter Titrant . . . . . . . . . . . . . .PAO Concentration [mol/L] . . . . . . . 0.00564 Formula t = . . . . . . . . . . . . xReport Output . . . . . . . . . . . . . . .Printer Results . . . . . . . . . . . . . .Yes All results . . . . . . . . . . . .Yes Raw results . . . . . . . . . . . .No Table of values . . . . . . . . . .No Sample data . . . . . . . . . . . .No E - V curve . . . . . . . . . . . .Yes dE/dV - V curve . . . . . . . . . .No d2E/dV2 - V curve . . . . . . . . .No log dE/dV - V curve . . . . . . . .No E - t curve . . . . . . . . . . . .No V - t curve . . . . . . . . . . . .No dV/dt - t curve . . . . . . . . . .No

MethodMethod 3341 free available cholorine residual Version 06-Jun-2002 2:50 pm

Title Method ID . . . . . . . . . . . .3341 Title . . . . . . . . . . . . . free av. chl. rs. Date/time . . . . . . . . . . . .06-Jun-2002 2:50Sample Sample ID . . . . . . . . . . . . Waste water Entry type . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . .200.0 Molar mass M . . . . . . . . . . . 70.90 Equivalent number z . . . . . . . 2 Titration stand . . . . . . . . . ST20A Pump . . . . . . . . . . . . . No Pump . . . . . . . . . . . . . No Rinse . . . . . . . . . . . . .Yes Solvent . . . . . . . . . .H2O Volume[mL] . . . . . . . . 20.0 Conditioning . . . . . . . . . No Temperatur sensor . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . 20EQP Titration (Ipol/Upol) Titrant/Sensor Titrant . . . . . . . . . . . .PAO Concentration [mol/L] . . . . 0.00564 Sensor . . . . . . . . . . . . DM143 Indication . . . . . . . . . . . . Amperometric Upol [mV] . . . . . . . . . . .500.0 Predispensing . . . . . . . . . . No Titrant addition dV [mL] . . . . . . . . . . . . 0.06 Measure mode . . . . . . . . . . . Timed increment dt [s] . . . . . . . . . . . . .20.0 Recognition Threshold . . . . . . . . . . . 0.0 Steepest jump only . . . . . . .Yes Range . . . . . . . . . . . . . .No Tendency . . . . . . . . . . . .None Termination at maximum volume [mL] . . . . . 1.2 at potential . . . . . . . . . .No at slope . . . . . . . . . . . .No after number EQPs . . . . . . . .No comb. termination conditions . .No Evaluation Procedure . . . . . . . . . . . .Segmented Potential 1 . . . . . . . . . . .No Potential 2 . . . . . . . . . . .No Stop for reevaluation . . . . . .NoCalculation Formula . . . . . . . . . . . . . .R1=Q*C1/m Constant . . . . . . . . . . . . . .C1=1000/z Decimal places . . . . . . . . . . .3 Result unit . . . . . . . . . . . .mmol/L Result name . . . . . . . . . . . .Cl2-Concentration Statistics . . . . . . . . . . . . .YesCalculation Formula . . . . . . . . . . . . . .R2=Q*C2/m Constant . . . . . . . . . . . . . .C2=1000*M/z Decimal places . . . . . . . . . . .3 Result unit . . . . . . . . . . . .mg/L Result name . . . . . . . . . . . .Cl2-Concentration Statistics . . . . . . . . . . . . .YesReport Output . . . . . . . . . . . . . . .Printer Results . . . . . . . . . . . . . .Yes All results . . . . . . . . . . . .Yes Raw results . . . . . . . . . . . .No Table of values . . . . . . . . . .Yes Sample data . . . . . . . . . . . .No E - V curve . . . . . . . . . . . .Yes dE/dV - V curve . . . . . . . . . .Yes d2E/dV2 - V curve . . . . . . . . .Yes log dE/dV - V curve . . . . . . . .No E - t curve . . . . . . . . . . . .No V - t curve . . . . . . . . . . . .No dV/dt - t curve . . . . . . . . . .No

120

M244

OCl-, HOCl, Cl3N, Cl2NR, ClNRR', ClNR2

Sodium acetate (anhydr., Fluka puriss, 82.04 g*mol-1)Acedic acid (Fluka puriss, 60.05 g*mol-1)KI (Fluka puriss, 166.01 g*mol-1); KIO3 (Fluka puriss, 214 g*mol-1)NaOH (Merck Titrisol, 1 M); HCl (Merck Titrisol, 1 M)Phenylarsine Oxide (Sigma, min. 97%, 168.0 g*mol-1)CHCl3 (Fluka purum, 119.38 g*mol-1)

0.00282 M Phenylarsine Oxide (PAO)(= 0.00564 N PAO)

DL5xRondo 60 with diaphragm pump

Cl2 in waste water --> OCl-, HOCl, Cl3N, Cl2NR, ClNRR', ClNR2,Cl-

ClIxNR3-x + 2 x KI-I + x H+ --> x KCl-I + x I20 + HxNR3-x + x K+

and HOClI (OCl-) + 2 KI-I + H+ --> KCl-I + I20 + K+ + H2O (OH-)

1 mol Cl2 corresponds to 1 mol I 2

C6H5AsIIIO + I2 + 2 H2O --> C6H7AsVO3 + 2 HI

KF Option Card ME-51 107 269250 mL Titration beakers ME-23829Printer

METTLER TOLEDO

Collect all arsine containinig solutionsin a separate, designated tank

Wastedisposal

Preparation and ProceduresChlorine treated waste waterSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DM 143Indication

Total residual chlorine in water according to ASTM D 1253 - 86

1) 250 mL 9.8 M Acetate buffer pH 4.0Weight in 36.625 g Sodium Acetate and 120 g Acedic acid and fill up to 250 mLwith dest. water

2) 250 mL 0.3 M KI:Weight in 12.5 g KI and fill up to 250 mL with dest. water.

3) 150 mL 0.3 M NaOH:Take 45 mL 1 M NaOH and add 105 mL of dest. water.

4) 100 mL 0.1 M HCl:Take 10 mL 1 M HCl and fill up to 100 mL with dest. water.

5) 1L 0.0047 M KIO 3:Weight in 1.0058 g KIO3 and fill up to 1L with dest. water.

6) 1L 0.00282 M Phenylarsine Oxide (PAO):Weight in 0.8 g PAO and add 150 mL 0.3 M NaOH. Even upon fast stirring not allthe PAO will dissolve. After settling, transfer 110 mL of the saturated solution into a1L measuring cylinder, add 800 mL dest. water and adjust the pH between 6 and7 using 0.1 M HCl. Fill up to 1L with dest. water and add 1 mL of CHCl 3 forpreservation.Standardize the resulting solution to 0.00282 M (0.00564 N) against 0.0047 M(0.0282 N) KIO3 in the following way:Take 0.5 mL 0.0047 M KIO3, add 150 mL dest. water, 5 mL 0.3 M KI and (shortlybefore the titration) 1 pipette of concentrated acedic acid. Titrate this sample withthe prepared PAO-solution using the titer-determination-method described in themethod section of application M 243.

7) Sample preparation:Take 200 mL sample and add shortly before the titration both 1 mL 9.8 M acetatebuffer pH 4.0 and 1 mL 0.3 M KI solution. To add one or both solutions long beforethe titration starts will falsify the results.

The method is reliable down to a Cl2-concentration of about 100ppb.Below this concentration the relative standard deviation (rsd) ofa sample series increases dramatically.However, the method is well suitable to (qualitatively) detecttraces of chlorine in waste water.

Method adjustment for different Cl2-Concentrations:

Titrant addition Termination dV [mL] at maximum volume [mL]

2 ppm Cl2: 0.3 3.0500 ppb Cl2: 0.06 1.2 (see method)100 ppb Cl2: 0.012 0.250 ppb Cl2: 0.006 0.1

Remarks

free available chlorine - conc. in mmol / LR1 = Q * C1 / m; C1 = 1000 / z

free available chlorine - conc. in mg / LR2 = Q * C2 / m; C2 = 1000 * M / z

Calculation

Determination of total residual chlorine (amount of available chlorine-induced oxidants present in water atany specified period, subsequent to the addition of chlorine) in chlorine treated water by direct amperometrictitration

Standard 0.0047 M KIO3 (= 0.0282 N KIO3)

Mike TreyerAuthor

121


Method 3340 total chlorine residual 06-Jun-2002 1:50 pmMeasured 06-Jun-2002 5:20 pmUser Mike Treyer

ALL RESULTS


1 Waste water 200.0 mL R1 = 0.007 mmol/L Cl2-Concentration R2 = 0.523 mg/L Cl2-Concentration2 Waste water 200.0 mL R1 = 0.007 mmol/L Cl2-Concentration R2 = 0.513 mg/L Cl2-Concentration3 Waste water 200.0 mL R1 = 0.007 mmol/L Cl2-Concentration R2 = 0.513 mg/L Cl2-Concentration

STATISTICS

Number of results R1 n = 3Mean value x = 0.007 mmol/L Cl2-ConcentrationStandard deviation s = 0.00008 mmol/L Cl2-ConcentrationRel. standard deviation srel = 1.118 %

Number of results R2 n = 3Mean value x = 0.516 mg/L Cl2-ConcentrationStandard deviation s = 0.00577 mg/L Cl2-ConcentrationRel. standard deviation srel = 1.118 %

Titration curve

Results

122

Method 3340 total cholorine residual Version 06-Jun-2002 1:50 pm

Title Method ID . . . . . . . . . . . .3340 Title . . . . . . . . . . . . . total chlorine residual Date/time . . . . . . . . . . . .06-Jun-2002 1:50Sample Sample ID . . . . . . . . . . . . Waste water Entry type . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . .200.0 Molar mass M . . . . . . . . . . . 70.90 Equivalent number z . . . . . . . 2 Titration stand . . . . . . . . . ST20A Pump . . . . . . . . . . . . . No Pump . . . . . . . . . . . . . No Rinse . . . . . . . . . . . . .Yes Solvent . . . . . . . . . .H2O Volume[mL] . . . . . . . . 20.0 Conditioning . . . . . . . . . No Temperatur sensor . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . 20EQP Titration (Ipol/Upol) Titrant/Sensor Titrant . . . . . . . . . . . .PAO Concentration [mol/L] . . . . 0.00564 Sensor . . . . . . . . . . . . DM143 Indication . . . . . . . . . . . . Amperometric Upol [mV] . . . . . . . . . . .500.0 Predispensing . . . . . . . . . . No Titrant addition dV [mL] . . . . . . . . . . . . 0.06 Measure mode . . . . . . . . . . . Timed increment dt [s] . . . . . . . . . . . . .20.0 Recognition Threshold . . . . . . . . . . . 0.0 Steepest jump only . . . . . . .Yes Range . . . . . . . . . . . . . .No Tendency . . . . . . . . . . . .None Termination at maximum volume [mL] . . . . . 1.2 at potential . . . . . . . . . .No at slope . . . . . . . . . . . .No after number EQPs . . . . . . . .No comb. termination conditions . .No Evaluation Procedure . . . . . . . . . . . .Segmented Potential 1 . . . . . . . . . . .No Potential 2 . . . . . . . . . . .No Stop for reevaluation . . . . . .NoCalculation Formula . . . . . . . . . . . . . .R1=Q*C1/m Constant . . . . . . . . . . . . . .C1=1000/z Decimal places . . . . . . . . . . .3 Result unit . . . . . . . . . . . .mmol/L Result name . . . . . . . . . . . .Cl2-Concentration Statistics . . . . . . . . . . . . .YesCalculation Formula . . . . . . . . . . . . . .R2=Q*C2/m Constant . . . . . . . . . . . . . .C2=1000*M/z Decimal places . . . . . . . . . . .3 Result unit . . . . . . . . . . . .mg/L Result name . . . . . . . . . . . .Cl2-Concentration Statistics . . . . . . . . . . . . .YesReport Output . . . . . . . . . . . . . . .Printer Results . . . . . . . . . . . . . .Yes All results . . . . . . . . . . . .Yes Raw results . . . . . . . . . . . .No Table of values . . . . . . . . . .Yes Sample data . . . . . . . . . . . .No E - V curve . . . . . . . . . . . .Yes dE/dV - V curve . . . . . . . . . .Yes d2E/dV2 - V curve . . . . . . . . .Yes log dE/dV - V curve . . . . . . . .No E - t curve . . . . . . . . . . . .No V - t curve . . . . . . . . . . . .No dV/dt - t curve . . . . . . . . . .No

Method

123

M258

Basic components

DIN ISO 3771 solventToluene/acetic acid/acetone600:300:100 mL in 1 L

Perchloric acid, HClO4 in acetic acid,c(HClO4) = 0.1 mol/L;

DL55, DL58DL70ES, DL77

Glass titration beaker ME-1014461 additional burette DV901 additional burette drive DV1010AT261 Balance, Olivetti Artjet 20 printer

METTLER TOLEDO

Special waste (aromatic compounds) Wastedisposal

Preparation and Procedures0.2-2 g OilSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DG113-SC with 0.4 mol/L TEAB in EtGIndication

Total Base Number according to DIN ISO 3771

General procedure:1. Blank determ. of solvent 3771. The blank is stored asauxiliary value H3 in mL (method b TBN).Therefore, it is not necessary to determine the titer before runningthe blank determination.2. Titer determination of 0.1 mol/L HClO4 in acetic acid withTHAM (M524).3. Determination of the total base number, TBN (Method TBN)

Sample determination:1) Weigh in a well homogenized oil sample in the titrationbeaker. The sample size is selected according to the expectedbase number:BN until 1: 2 gBN 15-30: 1 gBN more than 30: 0.25 g

2) 60 mL solvent 3771 needed to dissolve the sample areadded automatically with a second burette.

3) The electrolyte for the DG113 sensor is TEAB (Tetraethylammonium bromide)in ethylene glycol (EtG).To proceed withthis determination, the following steps are needed:1. Titer determination of perchloric acid (application M524)2. Blank of solvent 3771 (method )3. Sample titration.

Total base number according to DIN ISO 3771Consumption of mg KOH/g oil to the EQP.

ConditioningAfter every titration the electrode is conditioned in DIN ISO 3771.

Note:This application does not replace the standard DIN ISO 3771

Remarks

Base Number:R1 = (VEQ-H3)*c*t*C/m ; C1 = 56.1BN: mg KOH/g

R2 = VEQ ; mL

Calculation

Method for the determination of TBN (Total Base Number) according to DIN ISO 3771

Standard THAM, see application M524

C. De CaroAuthor

124


METTLER TOLEDO DL58 Titrator V2.4 Mettler-Toledo GmbH Market Support Laboratory

Method TBN TBN 30-04-2002 14:35Measured 30-04-2002 15:40User C. De Caro

RESULTS


1 01201 0.25725 g R1 = 74.18 mg KOH/g TBN R2 = 3.407 mL Consumption 2 01201 0.2323 g R1 = 74.03 mg KOH/g TBN R2 = 3.071 mL Consumption 3 01201 0.29195 g R1 = 74.11 mg KOH/g TBN R2 = 3.862 mL Consumption

STATISTICS Number results R1 n = 3 Mean value x = 74.10 mg KOH/gTBN Standard deviation s = 0.07412 mg KOH/gTBN Rel. standard deviation srel = 0.100 %

Additional results:

Oil n TBN srel

01204 3 9.85 0.2002301 2 9.38 --02302 2 10.90 --01201 3 74.10 0.1001202 2 17.13 --01206 3 13.92 0.18

Titration curve

Results

125

Method TBN TBN Version 30-04-2002 14:35

Title Method ID . . . . . . . . . . . . . TBN Title . . . . . . . . . . . . . . . TBN Date/time . . . . . . . . . . . . . 30-04-2002 14:35Sample Sample ID . . . . . . . . . . . . . 01201 Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.2 Upper limit [g] . . . . . . . . . 0.3 Molar mass M . . . . . . . . . . . . 100 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . TBN DIN 3771 Concentration [mol/L] . . . . . . . 0.1 Volumen [mL] . . . . . . . . . . . . 60Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 240EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . HClO4

Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . . . 0.5 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 1.0 dt [s] . . . . . . . . . . . . . 5.0 t(min) [s] . . . . . . . . . . . 10.0 t(max) [s] . . . . . . . . . . . 45.0 Recognition Threshold . . . . . . . . . . . . 200.0 Steepest jump only . . . . . . . Yes Range . . . . . . . . . . . . . . Yes Limit A [mV,pH,...] . . . . . 550 Limit B [mV,pH,...] . . . . . 900 Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 8.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R1=(VEQ-H3)*c*t*C/m Constant . . . . . . . . . . . . . . C1=56.1 Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg KOH/g Result name . . . . . . . . . . . . TBN Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of measured values . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

MethodMethod b TBN Blank with EQP Version 30-04-2002 9:59

Title Method ID . . . . . . . . . . . . . b TBN Title . . . . . . . . . . . . . . . Blank with EQP Date/time . . . . . . . . . . . . . 30-04-2002 9:59Sample Sample ID . . . . . . . . . . . . . DIN ISO 3771 Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 60.0 Molar mass M . . . . . . . . . . . . 100 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . TBN DIN 3771 Concentration [mol/L] . . . . . . . 0.1 Volumen [mL] . . . . . . . . . . . . 60Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . HClO4

Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DG113 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . . . 0.002 dV(max) [mL] . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . . 6.0 t(min) [s] . . . . . . . . . . . 10.0 t(max) [s] . . . . . . . . . . . 60.0 Recognition Threshold . . . . . . . . . . . . 200.0 Steepest jump only . . . . . . . Yes Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 0.1 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination conditions . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R1= VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Blank Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoAuxiliary value ID . . . . . . . . . . . . . . . . . Blank Formula . . . . . . . . . . . . . . H3=xReport Output unit . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . No Table of measured values . . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dV2 - V curve . . . . . . . . . No log dE/dV - V curve . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dV/dt - t curve . . . . . . . . . . No

126

M259

Amorphous precipitated silica,CTAB surface area: 85-275 m2/g

50 mL distilled waterpH buffers 7 and 10.

Aerosol OT,c(Aerosol OT) = 3.7 g / 2 L

DL50Graphix, DL53/DL55/DL58DL70ES, DL77AT261 Balance, printer

100 mL titration beaker ME-101974

METTLER TOLEDO


Preparation and Procedures1 mL of silica-CTAB sample solutionSample

Substance

Chemicals

Titrant

Instruments

Results

Chemistry

Accessories

DP550 with adapter cable ME-89600DG111

Indication

CTAB Surface Area on Amorphous Silica

General procedure:1) Titration of a known amount of CTAB solution (meth. 00032)2) The silica sample is prepared as indicated in the patent, andunadsorbed CTAB is titrated (1 mL sample size, meth. 00033).3) Calculation of the surface area, ACTAB (m

2/g)

CTAB Standard solution(Cetyltrimethylammonium bromide, CAS 57-09-0)Dissolve 11.000 +/- 0.001 g of reagent-grade CTAB in distilledwater in a 2 L volumetric flask. record the value as C.

Aerosol OT titrant solution(Sodium di(2-ethylhexyl) sulfosuccinate, CAS 577-11-7):Dissolve 3.70 g of Aerosol OT in distilled water in a 2 L flask.

Both solutions are kept in the dark for at least 12 days beforeuse (storage lives of the solutions: 2 months after preparation)

Sample preparation:The sample must be prepared according to the procedure bySwift at al. indicated in the US Patent 5.888.467 (1999).For more details, see under remarks.

Silica sample preparation:1) Add 0.500+/- 0.001 g silica as received in a 200 mL widemouth glass bottle. Record the value as S (g).2) 100 mL standard CTAB solution is added into the bottle.3) Add a stirring bar, close the bottle, stir gently for 15 minutes4) Place a calibrated pH electrode into the bottle and adjust thepH value to between 9.0 and 9.5.5) Cover the bottle with aluminium foil, and stir for 1 hour.6) The mixture is filtrated (0.2 or 0.45 µm filter). Note: theoriginal patent indicates to filtrate the sample for 30 minutes.7) 1 mL from the filtrated clear solution is taken and diluted with50 mL distilled water in a titration beaker.8) The sample is titrated with Aerosol OT solution to a turbiditymaximum endpoint ito determine the unadsorbed CTAB afterremoval of the colloidally dispersed silica.

The method has been modified with respect to the originaltitration procedure: Instead of performing a two-phase titration asdescribed by the patent, a direct turbidimetric titration was done.Automated two-phase titration did not provide any result, sincethe samples were too milky for an efficient EP recognition by thephotometric sensor.

Literature:US Patent 5.888.467, 30th March 1999, Swift et al.

Remarks

ACTAB = (V1-V2)*C*A*28.92/(V1*S*B)V1 = Titr. consumption for CTABV2 = Titr. consumption for CTAB-SilicaC = CTAB mass for standard sol. (g)A, B = Mass of a 1 g silica samplebefore/after drying (2 hours, 105°C).S = Silica sample mass (g)

Calculation

Titration of unadsorbed CTAB (cetyltrimethylammonium bromide) on amorphous precipitated silica.

Standard ---

C. De CaroAuthor

127


Method 00032 CTAB 15-04-2002 17:13 Measured 15-04-2002 18:06 User Cosimo

ALL RESULTS

No. ID Sample amount and results

1 CTAB 1.0 mL R1 = 3.707 ml Consumption 2 CTAB 1.0 mL R1 = 3.612 ml Consumption 3 CTAB 1.0 mL R1 = 3.645 ml Consumption 4 CTAB 1.0 mL R1 = 3.649 ml Consumption

STATISTICS Number results R1 n = 3 Mean value x = 3.636 mL Comsumption --> V 1

Standard deviation s = 0.02019 mL Comsumption Rel. standard deviation srel = 0.555 % Sample No. 1 deleted

Method 00033 Silica 2 + CTAB 19-04-2002 10:47 Measured 19-04-2002 11:54 User Cosimo

ALL RESULTS

No. ID Sample amount and results

1 Silica2CTAB 1.0 mL R1 = 3.045 ml Consumption 2 Silica2CTAB 1.0 mL R1 = 3.071 ml Consumption 3 Silica2CTAB 1.0 mL R1 = 3.054 ml Consumption 4 Silica2CTAB 1.0 mL R1 = 3.017 ml Consumption

STATISTICS Number results R1 n = 4 Mean value x = 3.047 mL Comsumption --> V 2

Standard deviation s = 0.02255 mL Comsumption Rel. standard deviation srel = 0.740 %

Titration curve

Results

128

Method 00032 CTAB Version 15-04-2003 17:13

Title Method ID . . . . . . . . . . . . . 00032 Title . . . . . . . . . . . . . . . CTAB Date/time . . . . . . . . . . . . . 15-04-2003 17:13Sample Sample ID . . . . . . . . . . . . . CTAB Entry type . . . . . . . . . . . . . Weight m Volume [mL] . . . . . . . . . . . 1.0 Molar mass M . . . . . . . . . . . . 1.0 Equivalent nuber z . . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 40 Time [s] . . . . . . . . . . . . . . 5EQP Titration Titrant/Sensor Titrant . . . . . . . . . . . . . Aerosol OT Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition Titrant addition . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . 0.2 Measure mode . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 10.0 t(max) [s] . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . 600.0 Steepest jump only . . . . . . Yes Range . . . . . . . . . . . . No Tendency . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . 5.0 at potential . . . . . . . . . No at slope . . . . . . . . . . . No after number EQPs . . . . . . No comb. termination conditions . No Evaluation Procedure . . . . . . . . . . Minimum Potential 1 . . . . . . . . . No Potential 2 . . . . . . . . . No Stop for reevaluation . . . . Yes Condition . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Calculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Report Output . . . . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes Tables of measured values . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dv2 - V curve . . . . . . . . . No log dE/dV -V curve . . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dv/dt - t curve . . . . . . . . . . No

MethodMethod 00033 Silica 2 + CTAB Version 19-04-2003 10:47

Title Method ID . . . . . . . . . . . . . 00033 Title . . . . . . . . . . . . . . . Silica 2 + CTAB Date/time . . . . . . . . . . . . . 19-04-2003 17:13Sample Sample ID . . . . . . . . . . . . . Silica2CTAB Entry type . . . . . . . . . . . . . Weight m Volume [mL] . . . . . . . . . . . 1.0 Molar mass M . . . . . . . . . . . . 1.0 Equivalent nuber z . . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperatur sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 40 Time [s] . . . . . . . . . . . . . . 5EQP Titration Titrant/Sensor Titrant . . . . . . . . . . . . . Aerosol OT Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition Titrant addition . . . . . . . . Dynamic dE(set) [mV] . . . . . . . . 8.0 dV(min) [mL] . . . . . . . . 0.02 dV(max) [mL] . . . . . . . . 0.2 Measure mode . . . . . . . . . . Equilibrium controlled dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 10.0 t(max) [s] . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . 600.0 Steepest jump only . . . . . . Yes Range . . . . . . . . . . . . No Tendency . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . 3.5 at potential . . . . . . . . . No at slope . . . . . . . . . . . No after number EQPs . . . . . . No comb. termination conditions . No Evaluation Procedure . . . . . . . . . . Minimum Potential 1 . . . . . . . . . No Potential 2 . . . . . . . . . No Stop for reevaluation . . . . Yes Condition . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Calculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . .Report Output . . . . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes Tables of measured values . . . . . Yes Sample data . . . . . . . . . . . . No E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . Yes d2E/dv2 - V curve . . . . . . . . . No log dE/dV -V curve . . . . . . . . . No E - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No dv/dt - t curve . . . . . . . . . . No

129


This application bulletin represents selected, possible application examples. These have been tested with all possiblecare in our lab with the analytical instrument mentioned in the bulletin. The experiments were conducted and theresulting data evaluated based on our current state of knowledge.

However, the application bulletin does not absolve you from personally testing its suitability for your intended methods,instruments and purposes. As the use and transfer of an application example are beyond our control, we cannot acceptresponsibility therefore.When chemicals and solvents are used, the general safety rules and the directions of the producer must beobserved.

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