Selected Applications

35
Application Brochure

Excellence Line Titrators

Selected Applications
for METTLER TOLEDO Titration Excellence Line
METTLER TOLEDO M363-A

Acid Number in Used Motor Oil According to ASTM D664-07

Titration Excellence Line: Method for the determination of the Acid Number (AN) and Strong Acid Number
(SAN) in used motor oil by potentiometric titration with potassium hydroxide in 2-propanol according to
ASTM D664-07.
Sample Used motor oil, Preparation and Procedures
approx. 3 g for AN 5 -10 1) The titer is determined using potassium hydrogen phthalate
(KHP): add approx. 80 mg KHP into a glass titration beaker
and dissolve it with 60 mL deion. water (See M363-F).
Substance Acid components as mg KOH/g
2) The buffer potential 1 (pH 4) and the buffer potential 2
sample, M=56.1 g/mol, z=1
(pH 11) are determined using aqueous pH buffers.
These values are stored as auxiliary values H[Buffer pH4] and
Chemicals 60 mL ASTM D664-07 solvent: H[Buffer pH11]. See M363-D (pH 11) and M363-E (pH 4).
Toluene:2-propanol:deion. water
500 mL : 495 mL : 5 mL 3) A blank value is determined for every new batch of solvent
mixture and stored as B[ASTM 664 AN] and B[ASTM 664 SAN]
See applications M363-B for AN and M363-C for SAN.
Titrant Potassium hydroxide in 2-propanol
KOH, c(KOH) = 0.1 mol/L 4) Depending on the AN of the sample, different sample
amounts are requested:
AN / mg KOH/g Sample size/g
0.05 - <1.0 20.0 +/- 2.0
Standard Potassium hydrogen phthalate, 80 mg
1.0 - <5.0 5.0 +/- 0.5
5 - <20 1.0 +/- 0.1
Instruments Titration Excellence T70/T90 20 - <100 0.25 +/- 0.02
Rondo20 with two membrane pumps 100 - <260 0.1 +/- 0.01
LabX Titration Software
5) After each sample titration the DG116-Solvent electrode is
Accessories DV1010 Burette rinsed and conditioned in a chloroform/toluene 1:1 mixture
Glass titration beaker ME-101446 during 5 minutes. Subsequently, it is conditioned in deionized
water during additional 5 minutes.
XS205 Balance
Olivetti JobJet 210 Printer
Remarks
Indication DGi116-Solvent 1) This application does not replace the ASTM standard.

2) The method parameters have been optimised for the sample

Chemistry KOH + HA = KA + H2O used in this application. Thus, it may be necessary to slightly
adapt the method to your specific sample.
HA: Acid components
3) The acid number indicates the amount of base as mg KOH/g
sample needed to titrate the acidic constituents in a sample
under specific conditions, i.e. specified solvent and endpoint.

Calculation R1= (Q-B[ASTM 664 AN])*C/m 4) The sample is titrated using an EQP method function. If no
C = M/z inflection point is detected, endpoints are taken at meter readings
corresponding to those found for aqueous acidic and basic
R2= QE(H[Buffer pH11])
buffer solutions for SAN at pH 4 and AN at pH 11
R3= (R2-B[ASTM 664 AN])*C/m
C = M/z 5) Calculations
R4 = QE(H[Buffer pH4]) R1 = AN to EQP in mg KOH/g
R5= (R4+B[ASTM 664 SAN])*C/m R2 = mmol consumption to buffer potential pH 11
Results C = M/z R3 = AN to buffer potential pH 11 in mg KOH/g
R4 = mmol consumption to buffer potential pH 4
Waste
Waste Dispose as aromatic organic solvent R5 = SAN to buffer potential pH 4 in mg KOH/g
disposal
disposal (toluene)
Literature:
- ASTM D664-07, see www.astm.org
- METTLER TOLEDO Appl. brochure 34, ME-51 725 066
- METTLER TOLEDO Appl. brochure 20, ME-51 725 020
Author Albert Aichert

7
Results
Summary Method-ID m363A
Sample
No. ID Sample size and results
1 Used oil 3.04742 g
R1 (TAN EQP) ----- mg KOH/g
R2 (Consumption BP) 0.376 mmol
R3 (TAN BP) 6.849 mg KOH/g
R4 (Consumption SAN) 0.011 mmol
R5 (SAN BP) 0.312 mg KOH/g
2 Used oil 3.31062 g
R1 (TAN EQP) ----- mg KOH/g
R2 (Consumption BP) 0.405 mmol
R3 (TAN BP) 6.796 mg KOH/g
R4 (Consumption SAN) 0.015 mmol
R5 (SAN BP) 0.355 mg KOH/g
3 Used oil 3.27543 g
R1 (TAN EQP) ----- mg KOH/g
R2 (Consumption BP) 0.402 mmol
R3 (TAN BP) 6.817 mg KOH/g
R4 (Consumption SAN) 0.015 mmol
R5 (SAN BP) 0.359 mg KOH/g
4 Used oil 3.09854 g
R1 (TAN EQP) ----- mg KOH/g
R2 (Consumption BP) 0.381 mmol
R3 (TAN BP) 6.826 mg KOH/g
R4 (Consumption SAN) 0.015 mmol
R5 (SAN BP) 0.379 mg KOH/g
5 Used oil 3.16791 g
R1 (TAN EQP) ----- mg KOH/g
R2 (Consumption BP) 0.388 mmol
R3 (TAN BP) 6.801 mg KOH/g
R4 (Consumption SAN) 0.016 mmol
R5 (SAN BP) 0.389 mg KOH/g
6 Used oil 3.27816 g
R1 (TAN EQP) ----- mg KOH/g
R2 (Consumption BP) 0.401 mmol
R3 (TAN BP) 6.794 mg KOH/g
R4 (Consumption SAN) 0.015 mmol
R5 (SAN BP) 0.358 mg KOH/g
Statistics
R3 TAN BP
Samples 6
Mean 6.814 mg KOH/g
s 0.021311 mg KOH/g
srel 0.313 %
R5 SAN BP
Samples 6
Mean 0.359 mg KOH/g
s 0.026553 mg KOH/g
srel 7.403 %

Table of measured values Titration curve

Volume Increment Signal Change 1st deriv. Time Temperature
mL mL mV mV mV/mL s °C
0 NaN 187 NaN NaN 0 25
0.05 0.05 181.1 -5.9 NaN 5 25
0.1 0.05 174.4 -6.7 NaN 10 25
0.153 0.053 167.3 -7.1 NaN 15 25
0.214 0.061 159.5 -7.8 NaN 20 25
0.278 0.064 151 -8.5 -131.19 25 25
0.337 0.059 143.4 -7.6 -130.39 30 25
0.4 0.063 135 -8.4 -131.91 36 25
0.46 0.06 127.3 -7.7 -133.33 41 25
0.521 0.061 118.9 -8.4 -135.08 46 25
0.578 0.057 111.3 -7.6 -137.04 51 25
0.639 0.061 102.6 -8.7 -138.96 56 25
0.692 0.053 95.5 -7.1 -140.91 61 25
0.754 0.062 86.5 -9 -142.71 66 25
0.806 0.052 79.2 -7.3 -145.46 71 25
0.865 0.059 70.5 -8.7 -146.73 76 25
0.916 0.051 63 -7.5 -147.09 81 25
0.972 0.056 54.7 -8.3 -145.08 86 25
1.023 0.051 47.2 -7.5 -141.58 91 25
1.08 0.057 39.5 -7.7 -137.1 97 25
1.144 0.064 30.8 -8.7 -131.48 102 25
1.204 0.06 23 -7.8 -127.32 108 25
1.266 0.062 15.4 -7.6 -124.03 114 25
1.336 0.07 6.7 -8.7 -120.47 119 25
1.399 0.063 -0.6 -7.3 -117.37 124 25
1.476 0.077 -9.8 -9.2 -113.94 130 25
1.538 0.062 -16.7 -6.9 -111.36 136 25
1.616 0.078 -25.2 -8.5 -109.72 142 25
1.693 0.077 -33.6 -8.4 -108.28 147 25
1.764 0.071 -41.1 -7.5 -106.87 152 25
1.844 0.08 -49.8 -8.7 -106.95 157 25
1.914 0.07 -57.5 -7.7 -104.32 163 25
1.987 0.073 -64.6 -7.1 -102.22 169 25
2.08 0.093 -74.3 -9.7 -100.26 174 25
2.149 0.069 -81.4 -7.1 -99.8 179 25
2.232 0.083 -88.7 -7.3 -98.69 184 25
2.334 0.102 -99.4 -10.7 -97.91 189 25
2.4 0.066 -105.9 -6.5 -96.27 194 25
2.484 0.084 -114 -8.1 -94.33 200 25
2.57 0.086 -121.5 -7.5 -91.47 205 25
2.67 0.1 -131 -9.5 -86.83 210 25
2.75 0.08 -137.5 -6.5 -85.12 215 25
2.86 0.11 -146.8 -9.3 -82.14 220 25
2.952 0.092 -154.2 -7.4 -80.26 225 25
3.059 0.107 -162.5 -8.3 -77.69 230 25
3.164 0.105 -171.1 -8.6 -76.36 235 25
3.257 0.093 -177.6 -6.5 -74.67 240 25
3.39 0.133 -187.7 -10.1 -73.03 245 25
3.488 0.098 -194.5 -6.8 -71.37 250 25
3.614 0.126 -203.7 -9.2 -70.21 255 25
3.717 0.103 -210.7 -7 -69.31 260 25
3.845 0.128 -219.5 -8.8 -66.44 266 25
3.957 0.112 -226.6 -7.1 -64.23 271 25
4.098 0.141 -236.1 -9.5 -60.27 276 25
4.21 0.112 -242.2 -6.1 -57.67 282 25
4.39 0.18 -252 -9.8 -53.15 288 25
4.536 0.146 -259.9 -7.9 -49.99 294 25
4.686 0.15 -266.7 -6.8 -46.27 300 25
4.886 0.2 -276 -9.3 -41.8 305 25
5.051 0.165 -282.3 -6.3 -37.81 310 25
5.251 0.2 -289.7 -7.4 -33.28 315 25
5.451 0.2 -295.5 -5.8 -29.4 320 25
5.651 0.2 -301.3 -5.8 -25.75 325 25
5.851 0.2 -306.1 -4.8 -23 330 25
6.051 0.2 -310.4 -4.3 -20.38 336 25
6.251 0.2 -314.3 -3.9 NaN 341 25
6.451 0.2 -317.7 -3.4 NaN 346 25
6.651 0.2 -320.9 -3.2 NaN 351 25
6.851 0.2 -323.6 -2.7 NaN 356 25
7.051 0.2 -326.2 -2.6 NaN 361 25

8
Method
Method m363 SAN & AN ASTM D664 29.01.2008 008 Conditioning
Author Albert Aichert Type Fix
Interval 1
001 Title Position Conditioning beaker
Type General titration Time 300 s
Compatible with T70 / T90 Speed 30 %
ID m363 Condition no
Title SAN & AN ASTM D664 009 Calculation R1
Author Albert Aichert Result TAN (EQP)
Date/Time 29.01.2008 10:12:42 Result unit mg KOH/g
Modified -- Formula R1=(Q-B[ASTM 664 AN])*C/m
Modified by -- Constant C z/M
Protect No M M[Potassium hydroxid]
SOP None z z[Potassium hydroxid]
Decimal places 3
002 Sample Result limits No
Number of IDs 1 Record statistics Yes
ID 1 Used oil Extra statistical
Entry type Weight functions No
Lower limit 1.0 g Send to buffer No
Upper limit 10.0 g Condition No
Density 1.0 g/mL 010 Calculation R2
Correction factor 1.0 Result Consumption EP
Temperature 25.0°C Result unit mmol
Entry Arbitrary Formula R2=QE(H[Buffer pH11])
Constant C 1
003 Titration stand (Rondo/Tower A) M M[none]
Type Rondo/Tower A z z[none]
Titration stand Rondo60/1A Decimal places 3
Result limits No
004 Pump Record statistics No
Auxiliary reagent ASTM 664 solvent Extra statistical
Volume 60 mL functions No
Condition No Send to buffer No
005 Stir Condition No
Speed 35 % 011 Calculation R3
Duration 60 s Result TAN (BP)
Condition No Result unit mg KOH/g
Formula R3=(R2-B[ASTM 664 AN])*C/m
006 Titration (EQP) [1] Constant C z/M
Titrant M M[Potassium hydroxid]
Titrant KOH in 2-Propanol z z[Potassium hydroxid]
Concentration 0.1 mol/L Decimal places 3
Sensor Result limits No
Type pH Record statistics Yes
Sensor DG116-SC Extra statistical
Unit mV functions No
Temperature acquisition Send to buffer No
Temperature acquisition No Condition No
Stir 012 Calculation R4
Speed 30 % Result Consumption SAN
Predispense Result unit mmol
Mode None Formula R4=QE(H[Buffer pH4])
Wait time 0 s Constant C 1
Control M M[none]
Control User z z[none]
Titrant addition Dynamic Decimal places 3
dE(set value) 8.0 mV Result limits No
dV(min) 0.05 mL Record statistics No
dV(max) 0.2 mL Extra statistical
Meas. value acquisition Equilibrium controlled functions No
dE 0.5 mV Send to buffer No
dt 1 s Condition No
t(min) 5 s 013 Calculation R5
t(max) 60 s Result SAN (BP)
Evaluation and recognition Result unit mg KOH/g
Procedure Standard Formula R5=(R4+B[ASTM 664 SAN])*C/m
Threshold 150 mV/mL Constant C z/M
Tendency None M M[Potassium hydroxid]
Ranges 1 z z[Potassium hydroxid]
Lower limit -400.0 mV Decimal places 3
Upper limit 0.0 mV Result limits No
Add. EQP criteria No Record statistics Yes
Termination Extra statistical
At Vmax 15.0 mL functions No
At potential Yes Send to buffer No
Potential H[Buffer pH11]-100 mV Condition No
Termination tendency None 014 Record
At slope No Summary No
After number of Results Per sample
recognized EQPs No Raw results Per sample
Number of EQPs No Table of meas. value No
Combined termination E - V Last titration function
criteria No dE/dV - V Last titration function
Accompanying stating Condition No
Accompanying stating No 015 End of sample
Condition
Condition No 016 Park
Titration stand Rondo60/1A
007 Conditioning Position Conditioning beaker
Type Fix Condition No
Interval 1 017 Record
Position Special beaker 1 Summary Yes
Time 180 s Results No
Speed 100 % Raw results No
Condition no Table of meas. value No
E - V No
dE/dV - V No
Condition No

9
METTLER TOLEDO M363-B

Blank Value for Acid Number According to ASTM D664-07

Titration Excellence Line: Method for the blank value determination to pH 11 of the acid number in the
solvent ASTM D664-07 with potassium hydroxide in 2-propanol.

Sample 60 mL solvent ASTM 664-07 Preparation and Procedures

mixture of 2-propanol/toluene/water in 1) Use the empty beaker for the blank determination. Add the
the ratio 495 mL : 500 mL : 5 mL solvent by means of the first membrane pump of Rondo 20.

Substance 2) For the blank determination, an EQP titration is used and the
--
result is calculated at the potential value obtained for pH 11
buffer, i.e. QE(H[Buffer pH11]).
This value was previously determined with application M363-D
Chemicals -- and stored as auxiliary value H[Buffer pH11].

3) Finally, the result QE(H[Buffer pH11]) in mmol is stored as

blank value B[ASTM 664 AN]

Titrant Potassium hydroxide in 2-propanol

KOH, c(KOH) = 0.1 mol/L

Standard Potassium hydrogen phthalate, 80 mg

Instruments Titration Excellence T50/T70/T90

Rondo20 with two membrane pumps
LabX Titration Software

Accessories DV1010 Burette

Glass titration beaker ME-101446
XS205 Balance
Olivetti JobJet 210 Printer
Remarks
Indication DGi116-Solvent 1) This application does not replace the ASTM standard.

2) The method parameters have been optimised for the sample

Chemistry KOH + HA = KA + H2O used in this application. Thus, it may be necessary to slightly
adapt the method to your specific sample.
HA: Acid components
3) The titrant has to be protected against the uptake of CO2 from
the air. NaOH on carrier (e.g. "Sodium hydroxide on support",
MERCK no. 101564, or "Sodium hydroxide on carrier", FLUKA
Nr. 03350) is an effective medium to avoid such formation of
Calculation R1= QE(H[Buffer pH11]) carbonate.

Literature:
- ASTM D664-07, see www.astm.org
- METTLER TOLEDO Appl. brochure 34, ME-51 725 066
- METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Results

Waste
Waste Dispose as aromatic organic solvent
disposal
disposal (toluene)

Author Albert Aichert

10
Results
Summary Method-ID T202
Sample
No. ID Sample size and results
1 Solvent 664 60 mL
R1 (Blank pH11) 0.003970
2 Solvent 664 60 mL
R1 (Blank pH11) 0.003941
3 Solvent 664 60 mL
R1 (Blank pH11) 0.004210
Statistics
R1 Blank pH11
Samples 3
Mean 0.004040 mmol
s 0.000148 mg KOH/g
srel 3.654 %

Table of measured values Titration curve

Volume Increment Signal Change 1st deriv. Time Temperature
mL mL mV mV mV/mL s °C
0 NaN -189.2 NaN NaN 0 25
0.002 0.002 -177.9 11.3 NaN 10 25
0.004 0.002 -171.9 6 NaN 20 25
0.009 0.005 -169 2.9 NaN 31 25
0.019 0.01 -168.7 0.3 NaN 41 25
0.029 0.01 -172.8 -4.1 NaN 52 25
0.039 0.01 -189.4 -16.6 NaN 62 25
0.044 0.005 -256.5 -67.1 NaN 87 25

11
Method
Method T202 Blank AN pH11 ASTM D664 07.12.2007 008 Calculation R1
Author Albert Aichert Result Blank pH11
Result unit mmol
001 Title Formula R1=QE(H[Buffer pH11])
Type General titration Constant C 1
Compatible with T50 / T70 / T90 M M[None]
ID T202 z z[None]
Title Blank AN pH11 ASTM D664 Decimal places 6
Author Albert Aichert Result limits No
Date/Time 07.12.2007 10:12:42 Record statistics Yes
Modified -- Extra statistical
Modified by -- functions No
Protect No Send to buffer No
SOP None Condition No
009 Blank
002 Sample Name ASTM 664 AN
Number of IDs 1 Value B= Mean[R1]
ID 1 Solvent 664 Unit mmol
Entry type Fixed volume Limits No
Volume 60 mL Condition No
Density 1.0 g/mL 010 Record
Correction factor 1.0 Summary No
Temperature 25.0°C Results Per sample
Entry Arbitrary Raw results Per sample
Table of meas. value No
003 Titration stand (Rondo/Tower A) E - V Last titration function
Type Rondo/Tower A dE/dV - V Last titration function
Titration stand Rondo60/1A Condition No
011 End of sample
004 Pump
Auxiliary reagent ASTM 664 solvent 012 Park
Volume 60 mL Titration stand Rondo60/1A
Condition No Position Conditioning beaker
Condition No
005 Stir 013 Record
Speed 35 % Summary Yes
Duration 60 s Results No
Condition No Raw results No
Table of meas. value No
006 Titration (EQP) [1] E - V No
Titrant dE/dV - V No
Titrant KOH in 2-Propanol Condition No
Concentration 0.1 mol/L
Sensor
Type pH
Sensor DG116-SC
Unit mV
Temperature acquisition
Temperature acquisition No
Stir
Speed 30 %
Predispense
Mode None
Wait time 0 s
Control
Control User
Titrant addition Dynamic
dE(set value) 12.0 mV
dV(min) 0.002 mL
dV(max) 0.01 mL
Meas. value acquisition Equilibrium controlled
dE 0.5 mV
dt 1 s
t(min) 10 s
t(max) 60 s
Evaluation and recognition
Procedure Standard
Threshold 200 mV/mL
Tendency Negative
Ranges 0
Add. EQP criteria No
Termination
At Vmax 15.0 mL
At potential Yes
Potential H[Buffer pH11]-30 mV
Termination tendency None
At slope No
After number of
recognized EQPs No
Number of EQPs No
Combined termination
criteria No
Accompanying stating
Accompanying stating No
Condition
Condition No
007 Rinse
Auxiliary reagent ASTM 664 solvent
Rinse cycles 1
Vol. per cycle 15 mL
Position Actual sample
Drain No
Condition No

12
METTLER TOLEDO M363-C

Blank Value for Strong Acid Number According to ASTM D664-07

Titration Excellence Line: Method for the blank value determination to pH 4 in the solvent ASTM D664-07
with hydrochloric acid in 2-propanol.

Sample 60 mL solvent ASTM 664-07 Preparation and Procedures

mixture of 2-propanol/toluene/water in 1) Use the empty beaker for the blank determinaton. Add the
the ratio 495 mL : 500 mL : 5 mL solvent by means of the first membrane pump of Rondo 20.

Substance 2) For the blank determination, an EQP titration is used and the
--
result is calculated at the potential value obtained for pH 4
buffer, i.e. QE(H[Buffer pH4]).
This value was previously determined with application M363-E
Chemicals -- and stored as auxiliary value H[Buffer pH4]

3) Finally, the result QE(H[Buffer pH4]) in mmol is stored as

blank value B[ASTM 664 SAN].

Titrant Hydrochloric acid in 2-Propanol

HCl, c(HCl) = 0.1 mol/L

Standard Tris-(hydroxymethyl)-aminomethane, 80 mg

Instruments Titration Excellence T50/T70/T90

Rondo20 with two membrane pumps
LabX Titration Software

Accessories DV1010 Burette

Glass titration beaker ME-101446
XS205 Balance
Olivetti JobJet 210 Printer
Remarks
Indication DGi116-Solvent 1) This application does not replace the ASTM standard.

2) The method parameters have been optimised for the sample

Chemistry KOH + HA = KA + H2O used in this application. Thus, it may be necessary to slightly
adapt the method to your specific sample.
HA: Acid components
Literature:
- ASTM D664-07, see www.astm.org
- METTLER TOLEDO Appl. brochure 34, ME-51 725 066
Calculation R1= QE(H[Buffer pH4]) - METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Results

Waste
Waste Dispose as aromatic organic solvent
disposal
disposal (toluene)

Author Albert Aichert

13
Results
Summary Method-ID T212
Sample
No. ID Sample size and results
1 solvent 664 60 mL
R1 (Blank pH4) 0.006157
2 solvent 664 60 mL
R1 (Blank pH4) 0.005933
3 solvent 664 60 mL
R1 (Blank pH4) 0.005929
4 solvent 664 60 mL
R1 (Blank pH4) 0.005733
Statistics
R1 Blank pH4
Samples 4
Mean 0.005938 mmol
s 0.000173 mg KOH/g
srel 2.918 %

Table of measured values Titration curve

Volume Increment Signal Change 1st deriv. Time Temperature
mL mL mV mV mV/mL s °C
0 NaN 44.5 NaN NaN 0 25
0.002 0.002 67.8 23.3 NaN 10 25
0.004 0.002 80 12.2 NaN 20 25
0.008 0.004 92.6 12.6 NaN 30 25
0.016 0.008 107.1 14.5 NaN 41 25
0.026 0.01 120.8 13.7 997.3 51 25
0.036 0.01 133.2 12.4 1010.34 62 25
0.046 0.01 146.5 13.3 1673.72 72 25
0.054 0.008 161.2 14.7 2863.48 82 25
0.06 0.006 175.6 14.4 NaN 92 25
0.062 0.002 187.1 11.5 NaN 103 25
0.064 0.002 197.4 10.3 NaN 113 25
0.066 0.002 210.7 13.3 NaN 124 25
0.068 0.002 227.6 16.9 NaN 134 25

14
Method
Method T212 Blank SAN pH4 ASTM D664 17.01.2008 008 Calculation R1
Author Albert Aichert Result Blank pH4
Result unit mmol
001 Title Formula R1=QE(H[Buffer pH4])
Type General titration Constant C 1
Compatible with T50 / T70 / T90 M M[None]
ID T212 z z[None]
Title Blank SAN pH4 ASTM D664 Decimal places 6
Author Albert Aichert Result limits No
Date/Time 17.01.2008 10:12:42 Record statistics Yes
Modified -- Extra statistical
Modified by -- functions No
Protect No Send to buffer No
SOP None Condition No
009 Blank
002 Sample Name ASTM 664 SAN
Number of IDs 1 Value B= Mean[R1]
ID 1 Solvent 664 Unit mmol
Entry type Fixed volume Limits No
Volume 60 mL Condition No
Density 1.0 g/mL 010 Record
Correction factor 1.0 Summary No
Temperature 25.0°C Results Per sample
Entry Arbitrary Raw results Per sample
Table of meas. value No
003 Titration stand (Rondo/Tower A) E - V Last titration function
Type Rondo/Tower A dE/dV - V Last titration function
Titration stand Rondo60/1A Condition No
011 End of sample
004 Pump
Auxiliary reagent ASTM 664 solvent 012 Park
Volume 60 mL Titration stand Rondo60/1A
Condition No Position Conditioning beaker
005 Stir Condition No
Speed 35 % 013 Record
Duration 60 s Summary Yes
Condition No Results No
Raw results No
006 Titration (EQP) [1] Table of meas. value No
Titrant E - V No
Titrant HCl in 2-propanol dE/dV - V No
Concentration 0.1 mol/L Condition No
Sensor
Type pH
Sensor DG116-SC
Unit mV
Temperature acquisition
Temperature acquisition No
Stir
Speed 30 %
Predispense
Mode None
Wait time 0 s
Control
Control User
Titrant addition Dynamic
dE(set value) 12.0 mV
dV(min) 0.002 mL
dV(max) 0.01 mL
Meas. value acquisition Equilibrium controlled
dE 0.5 mV
dt 1 s
t(min) 10 s
t(max) 60 s
Evaluation and recognition
Procedure Standard
Threshold 200 mV/mL
Tendency Positive
Ranges 0
Add. EQP criteria No
Termination
At Vmax 15.0 mL
At potential Yes
Potential H[Buffer pH4]+50 mV
Termination tendency None
At slope No
After number of
recognized EQPs No
Number of EQPs No
Combined termination
criteria No
Accompanying stating
Accompanying stating No
Condition
Condition No

007 Rinse
Auxiliary reagent ASTM 664 solvent
Rinse cycles 1
Vol. per cycle 15 mL
Position Actual sample
Drain No
Condition No

15
METTLER TOLEDO M363-D

Buffer Value pH 11 for Acid Number According to ASTM D664-07

Titration Excellence Line: Determination of the potential value for pH 11 buffer (AN, Acid Number) acccording
to ASTM D 664-07.

Sample 50 mL pH 11 buffer solution Preparation and Procedures

1) Always use fresh pH 11 buffer solution. The buffer pH 11 is
not stable when exposed to air.

Substance 2) 50 mL pH 11 buffer solution are added into a titration

--
beaker.

3) Before measure the buffer potential, the electrode should

Chemicals -- conditioned in aquous media (water pH 5-6) for 3 - 5 minutes.

4) The measured potential value for buffer pH 11 is stored as

auxilliary value H[Buffer pH11].

Titrant -- 5) Finally, the electrode is parked in the condioning beaker

containing slightly acidic water (pH 5-6).

Standard --

Instruments Titration Excellence T50/T70/T90

Rondo20 with two membrane pumps
LabX Titration Software

Accessories DV1010 Burette

Glass titration beaker ME-101446
XS205 Balance
Olivetti JobJet 210 Printer
Remarks
Indication DGi116-Solvent 1) This application does not replace the ASTM standard.

2) The buffer pH 11 is not stable when exposed to air. In fact,

Chemistry -- due to the high alkaline pH value, the absorption of CO2 from the
air is strongly improved.
For instance, the potential value (mV) in an open beaker with
buffer pH 11.can change of 0.1 mV/min
The potential value of an opened bottle of pH 11 buffer solution
can rapidly change.
Thus, it is very important to use fresh pH 11 buffer solution every
Calculation R1= E time a new value has to be determined

Literature:
- ASTM D664-07, see www.astm.org
- METTLER TOLEDO Appl. brochure 34, ME-51 725 066
- METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Results

Waste
Waste Neutralize before final disposal as
disposal
disposal queous solution.

Author Albert Aichert

16
Results
Method-ID T102

Data / Time 07.01.2008 03:12:05 pm

All results
Sample 1/1 Buffer pH11
R1(Buffer pH11) -222.400 mV

Table of measured values Titration curve

17
Method
Method T102 Buffer value AN pH11 ASTM D664 17.12.2007
Author Albert Aichert

001 Title
Type General titration
Compatible with T50 / T70 / T90
ID T102
Title Buffer value AN pH11 ASTM
D664
Author Albert Aichert
Date/Time 17.12.2007 10:12:42
Modified --
Modified by --
Protect No
SOP None

002 Sample
Number of IDs 1
ID 1 Buffer pH11
Entry type Fixed volume
Volume 50 mL
Density 1.0 g/mL
Correction factor 1.0
Temperature 25.0°C
Entry Arbitrary

003 Titration stand (Rondo/Tower A)

Type Rondo/Tower A
Titration stand Rondo60/1A

004 Stir
Speed 35 %
Duration 300 s
Condition No

005 Measure (normal) [1]

Sensor
Type pH
Sensor DG116-SC
Unit mV
Temperature acquisition
Temperature acquisition No
Stir
Speed 30 %
Acquisition of the measured value
Acquisition Fix
Time 30 s
Mean value No
t(min) 10 s
t(max) 60 s
Condition
Condition No

006 Calculation R1
Result Buffer pH11
Result unit mV
Formula R1=E
Constant C 1
M M[None]
z z[None]
Decimal places 3
Result limits No
Record statistics No
Extra statistical
functions No
Send to buffer No
Condition No

007 Auxiliary value

Name Buffer pH11
Value B= R1
Unit mV
Limits No
Condition No

008 Record
Summary No
Results Per sample
Raw results Per sample
Table of meas. value No
E - V No
dE/dV - V No
Condition No

009 End of sample

010 Park
Titration stand Rondo60/1A
Position Conditioning beaker
Condition No

18
METTLER TOLEDO M363-E

Buffer Value pH4 for Strong Acid Number According to ASTM D664-07
Titration Excellence Line: Determination of the potential value for pH 4 buffer (SAN, Strong Acid Number)
acccording to ASTM D 664-07.

Sample 50 mL pH 4 buffer solution Preparation and Procedures

1) Always use fresh pH 4 buffer solution.

2) 50 mL pH 4 buffer solution are added into a titration beaker.

Substance --
3) Before measure the buffer potential, the electrode should
conditioned in aquous media (water pH 5-6) for 3 - 5 minutes.

Chemicals -- 4) The measured potential value for buffer pH 4 is stored as

auxilliary value H[Buffer pH4].

5) Finally, the electrode is parked in the condioning beaker

containing slightly acidic water (pH 5-6).
Titrant --

Standard --

Instruments Titration Excellence T50/T70/T90

Rondo20 with two membrane pumps
LabX Titration Software

Accessories DV1010 Burette

Glass titration beaker ME-101446
XS205 Balance
Olivetti JobJet 210 Printer
Remarks
Indication DGi116-Solvent 1) This application does not replace the ASTM standard.

2) Before measure the buffer potential, the electrode should

Chemistry -- conditioned in aqueous media (water pH 5-6) for 3 - 5
minutes.

Literature:
- ASTM D664-07, see www.astm.org
- METTLER TOLEDO Appl. brochure 34, ME-51 725 066
Calculation R1= E - METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Results

Waste
Waste Neutralize before final disposal as
disposal
disposal queous solution.

Author Albert Aichert

19
Results
Method-ID T112

Data / Time 17.01.2008 11:12:05 pm

All results
Sample 1/1 Buffer pH4
R1(Buffer pH4) 169.200 mV

Table of measured values Titration curve

20
Method
Method T112 Buffer value SAN pH4 ASTM D664 16.01.2008
Author Albert Aichert

001 Title
Type General titration
Compatible with T70 / T90
ID T112
Title Buffer value SAN pH4 ASTM
D664
Author Albert Aichert
Date/Time 16.01.2008 10:12:42
Modified --
Modified by --
Protect No
SOP None

002 Sample
Number of IDs 1
ID 1 Buffer pH4
Entry type Fixed volume
Volume 50 mL
Density 1.0 g/mL
Correction factor 1.0
Temperature 25.0°C
Entry Arbitrary

003 Titration stand (Rondo/Tower A)

Type Rondo/Tower A
Titration stand Rondo60/1A

004 Stir
Speed 35 %
Duration 300 s
Condition No

005 Measure (normal) [1]

Sensor
Type pH
Sensor DG116-SC
Unit mV
Temperature acquisition
Temperature acquisition No
Stir
Speed 30 %
Acquisition of the measured value
Acquisition Fix
Time 30 s
Mean value No
t(min) 10 s
t(max) 60 s
Condition
Condition No

006 Calculation R1
Result Buffer pH4
Result unit mV
Formula R1=E
Constant C 1
M M[None]
z z[None]
Decimal places 3
Result limits No
Record statistics No
Extra statistical
functions No
Send to buffer No
Condition No

007 Auxiliary value

Name Buffer pH4
Value B= R1
Unit mV
Limits No
Condition No

008 Record
Summary No
Results Per sample
Raw results Per sample
Table of meas. value No
E - V No
dE/dV - V No
Condition No

009 End of sample

010 Park
Titration stand Rondo60/1A
Position Conditioning beaker
Condition No

21
METTLER TOLEDO M363-F

Titer Determination of 0.1 mol/L KOH in 2-Propanol (ASTM D664-07)

Titration Excellence Line:
Method for the titer determination of 0.1 mol/L KOH in 2-Propanol according to ASTM D664-07.

Sample Primary standard Preparation and Procedures

Potassium hydrogen phthalate, 1) Weigh the primary standard into the glass titration beaker to
70 - 100 mg avoid electrostatic influence.

Substance 2) Add 50 mL CO 2-free deionized water to dissolve the sample.

Potassium hydrogen phthalate
M=204.23 g/mol z=1
3) After each sample titration, the eelctrode is rinsed with water
Chemicals 50 mL CO 2-free, deionized water 4) At the end of the titration, the electrode is parked in the
condioning beaker containing slightly acidic water (pH 5-6).

Titrant Potassium hydroxide in 2-propanol

KOH, c(KOH) = 0.1 mol/L

Standard Potassium hydrogen phthalate, 80 mg

Instruments Titration Excellence T50/T70/T90

Rondo20 with two membrane pumps
LabX Titration Software

Accessories DV1010 Burette

Glass titration beaker ME-101446
XS205 Balance
Olivetti JobJet 210 Printer
Remarks
Indication DGi116-Solvent 1) This application does not replace the ASTM standard.

2) The titrant has to be protected against the uptake of CO2 from

Chemistry KOH + K2HPO3 = H2O + 3K+ + PO43- the air. NaOH on carrier (e.g. "Sodium hydroxide on support",
MERCK no. 101564, or "Sodium hydroxide on carrier", FLUKA
Nr. 03350) is an effective medium to avoid such formation of
carbonate.

Literature:
Calculation R1= m/(VEQ*c*C) - ASTM D664-07, see www.astm.org
C=(10*p*z) - METTLER TOLEDO Appl. brochure 34, ME-51 725 066
- METTLER TOLEDO Appl. brochure 20, ME-51 725 020.
p: purity of standard

Results

Waste
Waste Neutralize before final disposal as
disposal
disposal aqueous solution.

Author Albert Aichert

22
Results
Summary Method-ID T001

Sample
No. ID Sample size and results
1 KHP 0.11936 g
R1 (Titer) 0.961720
2 KHP 0.12372 g
R1 (Titer) 0.961095
3 KHP 0.11054 g
R1 (Titer) 0.960251
4 KHP 0.11502 g
R1 (Titer) 0.960945

Statistics
R1 Titer
Samples 4
Mean 0.961003
s 0.000603
srel 0.063 %

Titer
Titrant KOH in 2-Propanol
New titer 0.96100

Table of measured values Titration curve

23
Method
Method m363F Titer of KOH in 2-propanol 02.10.2007 008 Calculation R1
Author Albert Aichert Result Titer
Result unit --
001 Title Formula R1=(m/(VEQ*c*C)
Type General titration Constant C M/(10*p*z)
Compatible with T50 / T70 / T90 M M[Potassium hydroxid]
ID m363F z z[Potassium hydroxid]
Title Titer of KOH in 2-propanol Decimal places 6
Author Albert Aichert Result limits No
Date/Time 02.10.2007 10:51:42 Record statistics Yes
Modified -- Extra statistical
Modified by -- functions No
Protect No Send to buffer No
SOP None Condition No

002 Sample (Titer) 009 Record

Titrant KOH in 2-Propanol Summary No
Concentration 0.1 mol/L Results Per sample
Standard KHP Raw results Per sample
Type of standard solid Table of meas. value No
Entry type Weight E - V Last titration function
Lower limit 0.07 g dE/dV - V Last titration function
Upper limit 0.12 g Condition No
Density 1.0 g/mL 010 End of sample
Correction factor 1.0
Temperature 25.0°C 011 Titer
Entry Arbitrary Titrant KOH in 2-Propanol
Concentration 0.1 mol/L
003 Titration stand (Rondo/Tower A) TITER= Mean[R1]
Type Rondo/Tower A Limits No
Titration stand Rondo60/1A Condition No

004 Pump 012 Park

Auxiliary reagent Water Titration stand Rondo60/1A
Volume 60 mL Position Conditioning beaker
Condition No Condition No
005 Stir
Speed 60 % 013 Record
Duration 60 s Summary Yes
Condition No Results No
Raw results No
006 Titration (EQP) [1] Table of meas. value No
Titrant E - V No
Titrant KOH in 2-Propanol dE/dV - V No
Concentration 0.1 mol/L Condition No
Sensor
Type pH
Sensor DG116-SC
Unit mV
Temperature acquisition
Temperature acquisition No
Stir
Speed 30 %
Predispense
Mode Volume
Volume 1.0 mL
Wait time 5 s
Control
Control User
Titrant addition Dynamic
dE(set value) 8.0 mV
dV(min) 0.005 mL
dV(max) 0.5 mL
Meas. value acquisition Equilibrium controlled
dE 1.0 mV
dt 1 s
t(min) 3 s
t(max) 60 s
Evaluation and recognition
Procedure Standard
Threshold 3.0 pH/mL
Tendency Positive
Ranges 0
Add. EQP criteria No
Termination
At Vmax 10.0 mL
At potential No
Tendency None
At slope No
After number of
recognized EQPs Yes
Number of EQP's 1
Number of EQPs No
Combined termination
criteria No
Accompanying stating
Accompanying stating No
Condition
Condition No

007 Rinse
Auxiliary reagent Water
Rinse cycles 1
Vol. per cycle 15 mL
Position Actual sample
Drain No
Condition No

24
METTLER TOLEDO M364-A

Base Number in Used Motor Oil According to ASTM D4739-06a

Titration Excellence Line: Method for the determination of the base number (BN) in oil by titration with
hydrochloric acid in 2-propanol according to ASTM D4739-06a.

Sample Used Motor oil, ~2.5 g Preparation and Procedures

1) Solvent preparation: ASTM D4739-06a solvent is prepared
by mixing 2-propanol, toluene, chloroform and water in the
following ratio: 10:10:10:0.3 (v/v).
Substance Alkaline components in oil expressed
2) The titer is determined by titration of previously standardized
as KOH, M=56.1 g/mol , z=1
KOH in 2-propanol solution. The latter has been standardized
using potassium hydrogen phthalate (KHP), see M364-D.
Chemicals 60 mL ASTM D4739-06a solvent
(see Preparation and Procedures) 3) The acidic (pH 3) and the alkaline (pH 10) aqueous buffer
pH 3 and pH 10 buffer solutions potentials are measured and stored as auxiliary values pH 3 (H
[Buffer pH3] ) and ( H[Buffer pH10] ).

Titrant HCl in 2-propanol, c(HCl)=0.1 mol/L 4) Blank values for the base number (BN) are determined for
KOH in 2-propanol, c(HCl)=0.1 mol/L every new batch of solvent mixture by titration with HCl in 2-
propanol to the buffer pH 3 potential.
For strong base number (SBN), the solvent is titrated with KOH
in 2-propanol to pH 10 pot. value. The result is stored as blank
Standard KOH in 2-propanol 0.1 mol/L / KHP
value ASTM D4739 (M364-B).

Instruments Titration Excellence T70/T90 5) Add the oil sample into the titration beaker. The appropriate
Rondo 20 Sample changer sample size is calculated according to the following formula:
1 additional dosing unit (20 mL) sample size (g) = 7/expected BN

Accessories DV1010 and DV1020 Burettes 6) 60 mL ASTM D4739-06a solvent are added using an
Titration beakers ME-101974 additional dosing unit. This step can be performed manually
using a dispenser or a graduated cylinder.
XS205 Balance, SP250 pump
PC with LabX Software
Remarks
Indication DGi116-Solvent This method allows a fully automated procedure using a
sample changer and an additional dosing unit. It can be
modified for manual operation. Select "Manual stand" in the
Chemistry HCl + KOH = Cl - + K+ + H 2O method function "Titration stand".

1) This application does not replace the ASTM standard.

KOH represents the alkaline
The method parameters have been optimised for the sample
components. used in this application. Thus, it may be necessary to slightly
adapt the method to your specific sample.

Calculation Base number mg KOH/g: 2) The base number BN is defined as the consumption of
R1=(Q-B[ASTM D4739])*C/m hydrochloric acid to a specific endpoint to neutralize the alkaline
C=M/z components of the oil. It is expressed as mg KOH/g sample:
- If an EQP is found between the acidic buffer potential value and
Base number mg KOH/g at acidic potential: a point 100 mV past this potential, then this will be the BN.
R2=(QE(H[Buffer pH3])-B[ASTM D4739])*C/m - If no EQP is found in this region, then the result is evaluated at
C=M/z the potential value of the acidic buffer.

Results 3) Between each sample it is necessary to condition the

electrode under stirring during 300 s in deion. water. The
Waste
Waste Dispose of as halogenated organic electrode is parked in buffer pH 4 (Rinse beaker).
disposal
disposal waste
Literature:
1) ASTM D4739-06a and draft next version, see www.astm.org
2) METTLER TOLEDO Appl. brochure 34, ME-51 725 066.
3) METTLER TOLEDO Appl. brochure 20, ME-51 725 020.
Author Melanie Nijman

25
Results
Mettler Toledo T90 Titrator Mettler Toledo AG
Market Support Laboratory
17.01.2008

Method M364_A Base Number According to ASTM D4739-06a

RESULTS with DG116-Solvent electrode

No. ID Sample size and results
1 Used Motor Oil 2.54656 g
R1 = 3.50 mg KOH/g Content (EQP)
R2 = 1.87 mg KOH/g Content (Buffer Potential)
2 Used Motor Oil 2.67162 g
R1 = 3.48 mg KOH/g Content (EQP)
R2 = 1.80 mg KOH/g Content (Buffer Potential)
3 Used Motor Oil 2.48459 g
R1 = 3.46 mg KOH/g Content (EQP)
R2 = 1.80 mg KOH/g Content (Buffer Potential)
4 Used Motor Oil 2.54055 g
R1 = 3.49 mg KOH/g Content (EQP)
R2 = 1.84 mg KOH/g Content (Buffer Potential)
5 Used Motor Oil 2.4121 g
R1 = 3.45 mg KOH/g Content (EQP)
R2 = 1.81 mg KOH/g Content (Buffer Potential)
6 Used Motor Oil 2.53271 g
R1 = 3.44 mg KOH/g Content (EQP)
R2 = 1.83 mg KOH/g Content (Buffer Potential)

STATISTICS
Number results R1 n = 6
Mean value x = 3.47 mg KOH/g Content (EQP)
Standard deviation s = 0.02 mg KOH/g Content (EQP)
Relative standard deviation srel = 0.682 %

Number results R2 n = 6
Mean value x = 1.82 mg KOH/g Content (Buffer Potential)
Standard deviation s = 0.03 mg KOH/g Content (Buffer Potential)
Relative standard deviation srel = 1.501 %

RESULTS with DG113-SC electrode

STATISTICS
Number results R1 n = 6
Mean value x = 3.46 mg KOH/g Content (EQP)
Standard deviation s = 0.06 mg KOH/g Content (EQP)
Relative standard deviation srel = 1.659 %

Number results R2 n = 6
Mean value x = 1.71 mg KOH/g Content (Buffer Potential)
Standard deviation s = 0.05 mg KOH/g Content (Buffer Potential)
Relative standard deviation srel = 3.072 %

Table of measured values Titration curve

26
Method
Method: m364A Base number ASTM D4739 17.01.2008 008 Calculation R1
User: Melanie Nijman Result Content EQP
Result Unit mg KOH/g
Formula R1=(Q-B[ASTM D4739])*C/m
001 Title
Constant C= M/z
Type General titration
M M[Potassium hydroxide]
Compatible with T70/ T90
z z[Potassium hydroxide]
ID m364A
Decimal places 2
Title Base number ASTM D4739
Result limits No
Author Melanie Nijman
Record statistics Yes
Date / Time 17.01.2008
Extra statistical functions No
Modified at 11.01.2008
Send to buffer No
Modified by Administrator
Condition No
Protect No
SOP None
009 Calculation R2
LabX SOP None
Result Content (Buffer Potential)
Result Unit mg KOH/g
002 Conditioning
Formula R1=(QE(H[Buffer pH3])
Titration stand Rondo60/1A
-B[ASTM D4739])*C/m
Position Conditioning beaker
Constant C= M/z
Time [s] 20
M M[Potassium hydroxide]
Speed [%] 30
z z[Potassium hydroxide]
Condition No
Decimal places 2
Result limits No
003 Sample
Record statistics Yes
Number of IDs 1
Extra statistical functions No
ID 1 Motor Oil
Send to buffer No
Entry Type Weight
Condition No
Lower limit [g] 0.0
Upper limit [g] 10.0
010 Rinse
Density [g/mL] 1.0
Auxiliary reagent ASTM D4739
Correction factor 1.0
Rinse cycles 3
Temperature [°C] 25.0
Vol. per cycle [mL] 20.0
Entry Arbitrary
Position Actual position
Drain Yes
004 Titration stand
Drain pump SP250
Type Rondo/Tower A
Condition No
Titration stand Rondo60/1A
Lid handling No
011 Conditioning
Type Fix
005 Dispense (normal) [1]
Interval 1
Titrant ASTM D4739 solvent
Position Conditioning beaker
Concentration [mol/L] 1
Time [s] 300
Volume [mL] 60
Speed [%] 30
Dosing rate [mL/min] 60.0
Condition No
Condition No

012 Record
006 Stir
Summary No
Speed [%] 35
Results Per series
Duration [s] 60
Raw results Per series
Condition No
Table of measured values Last titration function
Sample data Per series
007 Titration (EQP) [1]
Resource data No
Titrant
E - V Last titration function
Titrant HCl in 2-Propanol
dE/dV - V Last titration function
Concentration [mol/L] 0.1
log dE/dV - V No
Sensor
d2 E/dV2 - V No
Type pH
BETA - V No
Sensor DG116-Solvent
E - t No
Unit mV
V - t No
Temperature aquisition
dV/dt - t No
Temperature measurement No
T - t No
Stir
E - V & dE/dV - V No
Speed [%] 35
V - t & dV/dt - t No
Predispense
Method No
Mode Volume
Series data No
Volume 0.5
Condition No
Wait time [s] 60
Predispense
013 End of sample
Mode Volume
Volume [mL] 0.2
014 Park
Wait time [s] 5
Titration stand Rondo60/1A
Control
Position Rinse beaker
Control User
Titrant addition Incremental Condition No
dV (mL) 0.1
Mode Fixed time
dt [s] 90
Evaluation and Recognition
Procedure Standard
Threshold [mV/mL] 80.0
Tendency None
Ranges 1
Lower limit 1 [mV] H[Buffer pH3]
Upper limit 1 [mV] H[Buffer pH3]+100
Add. EQP criteria No
Termination
At Vmax [mL] 5.0
At potential Yes
Potential H[Buffer pH3]+140
Termination tendency Positive
At Slope No
After number of recognized EQPs No
Combined termination criteria No
Accompanying stating
Accompanying stating No
Condition
Condition No

27
METTLER TOLEDO M364-B

Blank Value of Base Number Solvent According to ASTM D4739-06a

Titration Excellence Line: Blank value determination of the base number BN solvent by titration with
hydrochloric acid or potassium hydroxide in 2-propanol according to ASTM D4739-06a.

Sample 60 mL solvent ASTM D4739-06a Preparation and Procedures

1) Solvent preparation:
ASTM D4739-06a solvent is prepared by mixing 2-propanol,
toluene, chloroform and water in the following ratio:
Substance 10 : 10 : 10 : 0.3 (v/v).
--
2) The titer is determined by titration of standardized KOH in 2-
propanol solution. The latter is standardized using potassium
Chemicals pH 3 and pH 10 buffer solutions hydrogen phthalate (KHP).

3) The acidic and the alkaline aqueous buffers are measured

and stored as auxiliary values H[Buffer pH3] (BN) and H[Bufffer
pH10] (SBN, Strong Base Number). The values are then used
Titrant HCl in 2-propanol, c(HCl)=0.1 mol/L for the EQP termination and the calculation R1.
KOH in 2-propanol, c(HCl)=0.1 mol/L
4) 60 mL ASTM D4739-06a solvent are added using an
additional dosing unit. This step can be performed manually
using a dispenser or a graduated cylinder.
Standard KOH in 2-propanol 0.1 mol/L / KHP
5) Blank value determinations are performed for every new
Instruments Titration Excellence T70/T90 batch of solvent by titration with HCl in 2-propanol to pH 3
Rondo 20 Sample changer potential value. The result is stored as blank B[ASTM D4739].
1 additional dosing unit (20 mL)
6) For SBN, the solvent is titrated with KOH in 2-propanol to pH
Accessories DV1010 and DV1020 Burettes 10 buffer potential value and stored as B[ASTM D4739 pH10].
Titration beakers ME-101974
XS205 Balance, SP250
PC with LabX Software
Remarks
Indication DGi116-Solvent This method allows a fully automated procedure using a sample
changer and an additional dosing unit. It can be modified for
manual operation. Select "Manual stand" in the method function
Chemistry -- "Titration stand".

1) This application does not replace the ASTM standard.

2) The base number BN is defined as the consumption of

hydrochloric acid to a specific endpoint to neutralize the alkaline
components of the oil. It is expressed as mg KOH/g sample:
Calculation Consumption of HCl in 2-Propanol up to - If an EQP is found between the acidic buffer potential value and
EQP or acidic potential value: a point 100 mV past this potential, then this will be the BN.
R1=Q (mmol) or - If no EQP is found in this region, then the result is evaluated at
R1=QE(H[Buffer pH3]) the potential value of the acidic buffer pH3.
SBN blank: Consumption of KOH in 2-
Propanol up to EQP/potential value: 3) Between each sample it is necessary to condition the
R1=Q (mmol) or electrode under stirring during 300 s in deion. water. The
R1=QE(H[Buffer pH10]) electrode is parked in buffer pH 4 (Rinse beaker).
Results
Literature:
Waste
Waste Dispose of as halogenated organic 1) ASTM D4739-06a and draft next version, see www.astm.org
disposal waste 2) METTLER TOLEDO Appl. brochure 34, ME-51 725 066.
disposal
3) METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Author Melanie Nijman

28
Results
Mettler Toledo T90 Titrator Mettler Toledo AG
Market Support Laboratory
17.01.2008

Method m364B Blank Base Number According to ASTM D4739-06a

Measured 17.01.2007

RESULTS
No. ID Sample size and results
1 ASTM D4739 Solvent 60.0 mL
R1 = 0.00478 mmol Consumption (Buffer potential)
R3 = 0.00469 mmol Consumption (EQP)
2 ASTM D4739 Solvent 60.0 mL
R1 = 0.00487 mmol Consumption (Buffer potential)
R3 = 0.00478 mmol Consumption (EQP)
3 ASTM D4739 Solvent 60.0 mL
R1 = 0.00484 mmol Consumption (Buffer potential)
R3 = 0.00474 mmol Consumption (EQP)
4 ASTM D4739 Solvent 60.0 mL
R1 = 0.00481 mmol Consumption (Buffer potential)
R3 = 0.00472 mmol Consumption (EQP)
5 ASTM D4739 Solvent 60.0 mL
R1 = 0.00482 mmol Consumption (Buffer potential)
R3 = 0.00474 mmol Consumption (EQP)

STATISTICS
Number results R1 n = 5
Mean value x = 0.00482 mmol Consumption (Buffer potential)
Standard deviation s = 0.00003 mmol Consumption (Buffer potential)
Relative standard deviation srel = 0.697 %

Number results R3 n = 5
Mean value x = 0.00473 mmol Consumption (EQP)
Standard deviation s = 0.00003 mmol Consumption (EQP)
Relative standard deviation srel = 0.694 %

Table of measured values Titration curve

29
Method
Method: m364B Blank BN According to ASTM 17.01.2008 009 Calculation R3
User: Nijman Result Consumption (EQP)
Result Unit mmol
Formula R3=Q
001 Title
Constant C= 1
Type General titration
M M[None]
Compatible with T70/ T90
z z[None]
ID M364_B
Decimal places 5
Title Blank ASTM D4739
Result limits No
Author Mettler Toledo
Record statistics Yes
Date / Time 17.01.2008
Extra statistical functions No
Modified at 17.01.2008
Send to buffer No
Modified by Administrator
Condition No
Protect No
010 Record
SOP None
Summary No
LabX SOP
Results Per series
002 Conditioning
Raw results Per series
Titration stand Rondo60/1A
Table of measured values Last titration function
Position Conditioning beaker
Sample data Per series
Time [s] 20
Resource data No
Speed [%] 30
E - V Last titration function
Condition No
dE/dV - V Last titration function
003 Sample
log dE/dV - V No
Number of IDs 1
d2 E/dV2 - V No
ID 1 ASTM D4739 Solvent
BETA - V No
Entry Type Fixed volume
E - t No
Volume [mL] 60.0
V - t No
Density [g/mL] 1.0
dV/dt - t No
Correction factor 1.0
T - t No
Temperature [°C] 25.0
E - V & dE/dV - V No
004 Titration stand
V - t & dV/dt - t No
Type Rondo/Tower A
Method No
Titration stand Rondo60/1A
Series data No
Lid handling No
Condition No
005 Dispense (normal) [1]
011 Conditioning
Titrant ASTM D4739 solvent
Type Fix
Concentration [mol/L] 1
Interval 1
Volume [mL] 60
Position Conditioning beaker
Dosing rate [mL/min] 60.0
Time [s] 300
Condition No
Speed [%] 30
006 Stir
Condition No
Speed [%] 30
012 End of sample
Duration [s] 10
013 Park
Condition No
Titration stand Rondo60/1A
007 Titration (EQP) [1]
Position Rinse beaker
Titrant
Titrant HCl in 2-Propanol Condition No
Concentration [mol/L] 0.1 014 Blank
Sensor Name ASTM D4739
Type pH Value B= Mean[R1]
Sensor DG116-Solvent Unit mmol
Unit mV Limits No
Temperature aquisition Condition Yes
Temperature measurement No Formula Mean[R1]>0
Stir 015 Blank
Speed [%] 30 Name ASTM D4739
Predispense Value B= Mean[R3]
Mode Volume Unit mmol
Volume 0.02 Limits No
Wait time [s] 10 Condition Yes
Predispense Formula Mean[R3]>0
Mode Volume 016 Calculation R2
Volume [mL] 0.2 Result Mean Consumption (Buffer potential)
Wait time [s] 5 Result Unit mmol
Control Formula R2=Mean[R1]
Control User Constant C= 1
Titrant addition Incremental M M[None]
dV (mL) 0.002 z z[None]
Mode Fixed time Decimal places 5
dt [s] 30 Result limits No
Evaluation and Recognition Record statistics Yes
Procedure Standard Send to buffer No
Threshold [mV/mL] 7500.0 Condition No
Tendency Positive 017 Calculation R4
Ranges 0 Result Mean Consumption (EQP)
Add. EQP criteria No Result Unit mmol
Termination Formula R4=Mean[R3]
At Vmax [mL] 1.0 Constant C= 1
At potential Yes M M[None]
Potential H[Buffer pH3]+100 z z[None]
Termination tendency Positive Decimal places 5
At Slope No Result limits No
After number of recognized EQPs No Record statistics Yes
Combined termination criteria No Send to buffer No
Accompanying stating Condition No
Accompanying stating No 018 Record
Condition Summary No
Condition No Results Yes
008 Calculation R1 Raw results No
Result Consumption (Buffer potential) Resource data No
Result Unit mmol Calibration curve No
Formula R1=QE(H[Buffer pH3]) Method No
Constant C= 1 Series data No
M M[None] Condition No
z z[None]
Decimal places 5
Result limits No
Record statistics Yes
Extra statistical functions No
Send to buffer No

30
METTLER TOLEDO M364-C

Titer Determination of 0.1 mol/L HCl in 2-Propanol (ASTM D4739-06a)

Titration Excellence Line: Method for the titer determination of hydrochloric acid in 2-propanol according to
ASTM D4739-06a.

Sample Standardized KOH in 2-Propanol Preparation and Procedures

c(KOH) = 0.1 mol/L, 8.00 mL 1) Add 50 ml deionized into the titration beaker

2) 8 mL KOH in 2-propanol are added automaticlayy by menas

Substance ot an additional dosing unit. If this is not available, the sample
Potassium hydroxide, KOH
can be added manaully using a pipette.
M(KOH)=56.1 g/mol, z=1
3) The mean value of the titer determinations is saved
Chemicals 50 mL deionized water automatically as the titer for the titrant by means of the function
TITER in the method.

Titrant HCl in 2-propanol,

c(HCl)=0.1 mol/L

Standard KOH in 2-propanol 0.1 mol/L(via KHP)

Instruments Titration Excellence T50/T70/T90

Rondo 20 Sample changer
1 additional dosing unit

Accessories DV1010 Burettes

Titration beakers ME-101974
PC with LabX Software

Remarks
Indication DGi111-SC Literature:
1) ASTM D4739-06a and draft next version, see www.astm.org
2) METTLER TOLEDO Appl. brochure 34, ME-51 725 066.
Chemistry HCl + KOH = Cl - + K+ + H 2O 3) METTLER TOLEDO Appl. brochure 20, ME-51 725 020.

Calculation Titer HCl:

R1=VENDDi/(VEQ*c*C)
C=1/(cst*H[KOH Titer]*z)

The real value for the KOH concentration

determined in M364_D is used for the titer
determination of HCl in 2-Propanol.
Results

Waste
Waste Disposal as halogenated organic waste
disposal
disposal

Author Melanie Nijman

31
Results
Mettler Toledo T90 Titrator Mettler Toledo AG
Market Support Laboratory
07.03.2008

Method m364C Titer HCl in 2-Propanol

Measured 07.03.2008

RESULTS
No. ID Sample size and results
1 KOH in 2-Propanol 8.0 mL
R1 = 0.99689 -- Titer HCl
2 KOH in 2-Propanol 8.0 mL
R1 = 0.99622 -- Titer HCl
3 KOH in 2-Propanol 8.0 mL
R1 = 0.99649 -- Titer HCl
4 KOH in 2-Propanol 8.0 mL
R1 = 0.99674 -- Titer HCl
5 KOH in 2-Propanol 8.0 mL
R1 = 0.99613 -- Titer HCl
6 KOH in 2-Propanol 8.0 mL
R1 = 0.99626 -- Titer HCl
7 KOH in 2-Propanol 8.0 mL
R1 = 0.99694 -- Titer HCl

STATISTICS
Number results R1 n = 7
Mean value x = 0.99652 -- Titer HCl
Standard deviation s = 0.00033 -- Titer HCl
Relative standard deviation srel = 0.034 %

Table of measured values Titration curve

32
Method
Method: m364C Titer of HCl in 2-Propanol 07.03.2008 008 Record
User: Melanie Nijman Summary No
Results Per sample
Raw results Per sample
001 Title
Table of measured values Last titration function
Type Titer determination
Sample data No
Compatible with T50 / T70 / T90
Resource data No
ID M364_C
E - V Last titration function
Title Titer of HCl in 2-Propanol
dE/dV - V Last titration function
Author melanie Nijman
log dE/dV - V No
Date / Time 26.02.2008
d2 E/dV2 - V No
Modified at 07.03.2008
BETA - V No
Modified by Administrator
E - t No
Protect No
V - t No
SOP None
dV/dt - t No
LabX SOP
T - t No
E - V & dE/dV - V No
002 Sample (Titer)
V - t & dV/dt - t No
Titrant HCl in 2-Propanol
Method No
Concentration 0.1
Series data No
Standard KOH in 2-Propanol
Condition No
Type of standard liquid
Entry type Fixed volume
009 End of sample
Volume [mL] 8.0
Correction factor 1.0
010 Titer
Temperature [°C] 25.0
Titrant HCl in 2-Propanol
Concentration [mol/L] 0.1
003 Titration stand
TITER= Mean[R1]
Type Rondo/Tower A
Limits No
Titration stand Rondo60/1A
Lid handling No Condition No

004 Dispense (normal) [1] 011 Park

Titrant KOH in 2-Propanol Titration stand Rondo60/1A
Concentration [mol/L] 0.1 Position Conditioning beaker
Volume [mL] 8.0 Condition No
Dosing rate [mL/min] 60.0
Condition No 012 Calculation R2
Result Mean Titer
005 Stir Result Unit --
Speed [%] 30 Formula R2=Mean[R1]
Duration [s] 10 Constant C= 1
Condition No M M[None]
z z[None]
006 Titration (EQP) [1] Decimal places 5
Titrant Result limits No
Titrant HCl in 2-Propanol Record statistics Yes
Concentration [mol/L] 0.1 Send to buffer No
Sensor Condition No
Type pH
Sensor DG111-SC 013 Record
Unit pH Summary No
Temperature aquisition Results Yes
Temperature measurement No Raw results No
Stir Resource data No
Speed [%] 30 Calibration curve No
Predispense Method No
Mode None Series data No
Wait time [s] 0 Condition No
Control
Control User
Titrant addition Dynamic
dE (set value) 8.0
dV(min) [mL] 0.01
dV(max) [mL] 0.5
Mode Equilibrium controlled
dE 0.5
dt [s] 1
t(min) [s] 3
t(max) [s] 30
Evaluation and Recognition
Procedure Standard
Threshold [pH/mL] 3.0
Tendency None
Ranges 0
Add. EQP criteria No
Buffer capacity No
Termination
At Vmax [mL] 10.0
At potential No
At Slope No
After number of recognized EQPs Yes
Number of EQPs 1
Combined termination criteria No
Accompanying stating
Accompanying stating No
Condition
Condition No

007 Calculation R1
Result Titer
Result Unit --
Formula R1=VENDDi/(VEQ*c*C)
Constant C= 1/(cst*H[KOH Titer]*z)
M M[None]
z z[None]
Decimal places 5
Result limits No
Record statistics Yes
Extra statistical functions No

33
METTLER TOLEDO M364-D

Titer Determination of 0.1 mol/L KOH in 2-Propanol (ASTM D4739-06a)

Titration Excellence Line: Method for the titer determination of potassium hydroxide in 2-propanol according
to ASTM D4739-06a.

Sample Primary standard KHP Preparation and Procedures

m = ~ 0.11 g 1) weigh the standard into the glass titration beaker in order to
avoid electrostatic interferences.

Substance 2) Add 50 ml deionized into the titration beaker.

Potassium hydrogen phthalate
M = 204.23 g/mol; z=1
3) The mean value of the titer determinations is saved
automatically as the titer for the titrant by means of the function
Chemicals 50 mL deionized water TITER in the method.

Titrant KOH in 2-propanol

c(KOH) = 0.1 mol/L

Standard --

Instruments Titration Excellence T50/T70/T90

Rondo 20 Sample changer

Accessories DV1010 Burettes

Titration beakers ME-101974
PC with LabX Software

Remarks
Indication DGi111-SC 1) The titrant has to be protected against the uptake of CO2 from
the air.
NaOH on carrier (e.g. "Sodium hydroxide on support", MERCK
Chemistry KHC8H4O4 + KOH = H20 + K 2C 8H4O4 no. 101564, or "Sodium hydroxide on carrier", FLUKA Nr.
03350) is an effective medium to avoid such formation of
carbonate.

Literature:
1) ASTM D4739-06a and draft next version, see www.astm.org
Calculation Titer KOH: 2) METTLER TOLEDO Appl. brochure 34, ME-51 725 066.
3) METTLER TOLEDO Appl. brochure 20, ME-51 725 020.
R1=m/(VEQ*c*C)
C=M/(10*p*z)

Results

Waste
Waste Disposal as halogenated organic waste
disposal
disposal

Author Melanie Nijman

34
Results
Mettler Toledo T90 Titrator Mettler Toledo AG
Market Support Laboratory
28.02.2008

Method m364D Titer of KOH in 2-propanol

Measured 28.02.2008

RESULTS
No. ID Sample size and results
1 KHP 0.1057 g
R1 = 0.9870 -- Titer KOH
2 KHP 0.1030 g
R1 = 0.9920 -- Titer KOH
3 KHP 0.1018 g
R1 = 0.9960 -- Titer KOH
4 KHP 0.1209 g
R1 = 0.9900 -- Titer KOH
5 KHP 0.1183 g
R1 = 0.9920 -- Titer KOH
6 KHP 0.1205 g
R1 = 0.9930 -- Titer KOH

STATISTICS
Number results R1 n = 6
Mean value x = 0.992 -- Titer KOH
Standard deviation s = 0.003 -- Titer KOH
Relative standard deviation srel = 0.304 %

Table of measured values Titration curve

35
Method
Method: m364D Titer of KOH in 2-Propanol 28.02.2008 007 Record
User: Melanie Nijman Summary No
Results Per sample
Raw results Per sample
001 Title
Table of measured values Last titration function
Type Titer determination
Sample data No
Compatible with T50 / T70 / T90
Resource data No
ID M364_D
E - V Last titration function
Title Titer of KOH in 2-Propanol
dE/dV - V Last titration function
Author Melanie Nijman
log dE/dV - V No
Date / Time 26.02.2008
d2 E/dV2 - V No
Modified at 28.02.2008
BETA - V No
Modified by Administrator
E - t No
Protect No
V - t No
SOP None
dV/dt - t No
LabX SOP
T - t No
E - V & dE/dV - V No
002 Sample (Titer)
V - t & dV/dt - t No
Titrant KOH in 2-Propanol
Method No
Concentration 0.1
Series data No
Standard Potassium hydrogen phthalate
Condition No
Type of standard solid
Entry type Weight
008 End of sample
Lower limit 0.0
Upper limit 0.5
009 Titer
Correction factor 1.0
Titrant KOH in 2-Propanol
Temperature [°C] 25.0
Concentration [mol/L] 0.1
Input Arbitrary
TITER= Mean[R1]
Limits No
003 Titration stand
Type Rondo/Tower A Condition No
Titration stand Rondo60/1A
Lid handling No 010 Park
Titration stand Rondo60/1A
004 Stir Position Conditioning beaker
Speed [%] 30 Condition No
Duration [s] 30
Condition No 011 Calculation R2
Result Mean Titer
005 Titration (EQP) [1] Result Unit --
Titrant Formula R2=Mean[R1]
Titrant KOH in 2-Propanol Constant C= 1
Concentration [mol/L] 0.1 M M[None]
Sensor z z[None]
Type pH Decimal places 3
Sensor DG111-SC Result limits No
Unit pH Record statistics Yes
Temperature aquisition Send to buffer No
Temperature measurement No Condition No
Stir
Speed [%] 30 012 Auxiliary value
Predispense Name KOH Titer
Mode None Formula H= R2
Wait time [s] 0 Limits No
Control Condition No
Control User
Titrant addition Dynamic 013 Record
dE (set value) 8.0 Summary No
dV(min) [mL] 0.01 Results Yes
dV(max) [mL] 0.5 Raw results No
Mode Equilibrium controlled Resource data No
dE 0.5 Calibration curve No
dt [s] 1 Method No
t(min) [s] 3 Series data No
t(max) [s] 30 Condition No
Evaluation and Recognition
Procedure Standard
Threshold [pH/mL] 3.0
Tendency None
Ranges 0
Add. EQP criteria No
Buffer capacity No
Termination
At Vmax [mL] 10.0
At potential No
At Slope No
After number of recognized EQPs Yes
Number of EQPs 1
Combined termination criteria No
Accompanying stating
Accompanying stating No
Condition
Condition No

006 Calculation R1
Result Titer
Result Unit --
Formula R1=m/(VEQ*c*C)
Constant C= M/(10*p*z)
M M[Potassium hydrogen phthalate]
z z[Potassium hydrogen phthalate]
Decimal places 3
Result limits No
Record statistics Yes
Extra statistical functions No
Send to buffer No
Condition No

36