Titulacion Petroleum Industry

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Application Brochure
Titration Excellence
KF Compact Titrators
Workflow Automation
Selected Applications
Titration Analyses of Petroleum Products
Application Brochure 48
METTLER TOLEDO Application Brochure 48

Introduction
A large portion of the world’s economy depends on the petroleum industry which is the supplier of a lot of
different products. Refined petroleum products are used as energy source or to produce a variety of different fine
chemicals or plastic materials.
It is therefore primordial to precisely know the composition of all the raw and refined products. An easy way of
analyzing petroleum product is the use of titration. A lot of different parameters like acid number, base number,
bromine index, water content or mercaptan content can be measured with this technique.
METTLER TOLEDO Excellence Titratros are versatile instruments which can be modularly configured to determine
all the above mentioned parameters. A complete automation can be achieved using an InMotion autosampler or
a Karl Fischer automated oven, the InMotion KF.
This brochure summarizes the most relevant possible titration analyses on petroleum products and gives
several complete application examples. The most important international standards for titration of oil are listed
at the beginning of each chapter. Furthermore, a list of international standards for the measurement of density,
refractive index or UV/VIS spectrophotometry is presented at the end of the brochure.
Figure 1: Modularity of Titration Excellence instruments
Daniel Buchmann Dr. Nicolas Monney

Head Market Support Group Applications Chemist
SBU Analytical Chemistry Market Support Group


Content
CONTENT ...................................................................................................................... 5
ACID NUMBER DETERMINATION ...................................................................................... 3
Automated Acid Number Determination according to ASTM D664-11a .......................................................... 4
Acid Number in Crude Oil by Thermometric Titration According to ASTM D8045-2016 ................................. 12
Acid Number in Crude Oil by Thermometric Titration (ASTM D8045-2016): Titer and Blank ......................... 16
BASE NUMBER DETERMINATION ....................................................................................23
Automated Base Number Determination according to ASTM D4739 ............................................................. 24
Base Number Determination in Oil by Thermometric Titration ..................................................................... 30
Base Number Determination in Oil by Thermometric Titration: Titer and Blank ............................................. 36
BROMINE INDEX AND BROMINE NUMBER .......................................................................43
Bromine Index Determination According to ASTM D1492 (5 mA) ................................................................ 44
Automated Bromine Number Determination of Petrol According to ASTM D1159-01 .................................... 50
MERCAPTAN .................................................................................................................57
H2S and Mercaptan Sulfur Content in Petroleum Products According to UOP 163-10 ................................... 58
WATER CONTENT ..........................................................................................................67
Water Content of a Lubricant with InMotion KF ........................................................................................... 68
Automated Water Content Determination of Brake Fluid with InMotion KF .................................................... 74
REFINERY PROCESSES ..................................................................................................81
Total Hardness of Tap Water by Photometric Titration ................................................................................. 82
LIST OF STANDARDS .....................................................................................................88

Acid Number Determination
METTLER TOLEDO Page 2 of 91

Oil naturally contains acids, essentially related to sulfur compounds and aromatic or aliphatic acids. In used oil,
acid is produced by the burning of sulfur that produces sulfuric acid. Acidic oil is corrosive and can lead to
machine breakdown, pipeline leakage or pollution. It is therefore important to have a reliable determination of
acid content to help the planning of oil replacement, change oil only if needed and prevent corrosion.
The acid content of oil, the so-called acid number (AN), is expressed as the equivalent amount of potassium
hydroxide (KOH) needed to neutralize 1 g of sample and is given as mg KOH/g. The determination of AN is
performed by titration using KOH in 2-propanol as titrant. A potentiometric indication is generally used, but it is
also possible to use thermometric indication.
Numerous standards describe the titration of acid number. Among them, we have chosen two examples that are
described in this application brochure, the potentiometric method ASTM D664 and the thermometric method
ASTM D8045. A list of other standards for the determination of AN can be found in Table 1.
Standard Description of test Mettler-Toledo Titration methods

ASTM D664 Acid Number by Potentiometric Titration M726
ASTM D8045 Acid Number by Thermometric Titration M721 – M725
ASTM D974 Acid Number by Colorimetric Titration
ASTM D3242 Acidity in Aviation Turbine Fuel
DIN EN 12634 Acid Number in Petroleum Products
IP 177 Acid Number in Petroleum Products
IP 37 Acidity and Alkalinity of Lubricating Grease
ISO 6619 Acid Number by Potentiometric Titration
UOP 565 Acid Number of Petroleum Products/Distillates
Table 1: Standards for the determination of Acid Number
Potentiometric determinations of acid number are well established and used successfully for years. These
methods suffer however from several drawbacks: They are slow and the pH glass electrode needs an intensive
cleaning and time consuming conditioning steps go give accurate results. These problems are addressed with
thermometric titration, a fast technique where the thermometric sensor does not require systematic conditioning
to work efficiently. Thermometric AN determination can be up to 16 times faster than potentiometric AN.
However, when the potentiometric titration can be applied to almost any petroleum samples, thermometric
titration of AN can only be used with samples containing no or little additives. Additives can react with the
thermometric indicator rending the EQP impossible to find. This technique is for example well suited for crude
oil.
Three Acid Number determination methods are presented in the present brochure:
1. Potentiometric method according to ASTM D664, M726
2. Thermometric method according to ASTM D8045, M721
3. Thermometric method according to ASTM D8045, Titer and Blank determination, M726

M726 – Acid Number ASTM D664
Automated Acid Number Determination

according to ASTM D664-11a
Introduction
2. The buffer potentials are saved as auxiliary
The determination of the acid number plays a values
significant role in the quality control of petroleum 3. A new blank value is determined and stored
products to estimate the amount of additive for every new batch of solvent mixture.
depletion, acidic contamination and oxidation. 4. Special beakers 1-4, the rinse beaker and the
This note describes the potentiometric conditioning beaker on the InMotion Pro (100
determination of the acid number (AN) and strong mL beakers) have been used for rinsing and
acid number (SAN) in a motor oil sample regenerating the DGi113-SC:
according to ASTM D664. - Special beaker 1: Chloroform
- Special beaker 2: 2-Propanol
The acid number is the amount of base as mg - Special beaker 3: pH buffer 4.01
KOH/g sample needed to titrate the acidic - Conditioning beaker: ASTM D664 solvent
constituents in a sample. Analysis is performed - Rinse beaker: Power shower rinsing
using the InMotion Pro sample changer with Cover (SD660, SP280)
up lid-handling to cover the sample beakers prior - The optimal rinsing sequence for this
and after titration. SmartSample workflow ensures application was the following:
secure wireless sample weight and ID transfer 5. After titration – Conditioning beaker for 90 s –
from the balance to the titration system. Special beaker 1 for 180 s – Special beaker 2
Sample preparation and procedures for 90 s – Rinsing with H2O with power
shower – Special beaker 3 for 500 s –
1. Titer determination: add ~ 80 mg KHP into a Conditioning beaker for 30 s – Next Sample.
glass titration beaker with 60 mL deion.
water.

Chemistry Results
Acid compounds as mg KOH/g sample
R2: TAN EQP R4: TAN BP
M=56.1 g/mol, z=1 [mg KOH/g] [mg KOH/g]
1 1.466 1.442
KOH + HA = KA + H2O
2 ---* 1.420
HA: Acid components 3 1.333 1.419
4 1.410 1.479
5 1.344 1.413
Solutions 6 1.327 1.443
Titrant: Potassium hydroxide in 2-Propanol Mean 1.376 1.436
KOH, c(KOH) = 0.1 mol/L s 0.060 0.025
Chemicals: 60 ml ASTM D664 solvent: srel 4.386% 1.708%
Toluene : 2-Propanol : H2O * No EQP detected for this sample
(500 mL : 495 mL : 5 mL)
Standard: Potassium hydrogen phthalate, As the titration curve of the motor oil sample is
KHP, 80 mg rather flat, EQP detection is challenging. This is
reflected by the higher relative standard deviation
(srel) of TAN EQP with respect to the srel for
Instruments and accessories evaluation at fixed buffer potential pH11.
 Titration Excellence T7 (30252675) or Remarks

T9 (30252676) (T9 is used for
Depending on the AN of the sample, different
automatic calculations with "if….then"
sample amounts are recommended:
functionality)
 XPE205 Analytical balance Acid number Sample size
(30087653) [mg KOH/g] [g]
 InMotion Pro Base (30094122) 0.05 – 1.0 20.0 +/- 2.0
 InMotion Pro Rack Kit 100 mL 1.0 – 5.0 5.0 +/- 0.5
(30094131) 5.0 – 20.0 1.0 +/- 0.1
 Kit InMotion SmartSample (30094251) 20.0 – 100.0 0.25 +/- 0.02
 Lid Handler for InMotion Pro 100 mL
100.0 – 260.0 0.1 +/- 0.001
(30094254)
 SD660 membrane pump for power
shower rinsing (included in InMotion The acid number is the amount of base as mg
Pro Base delivery) KOH/g sample needed to titrate the acidic
 2 x SP280 peristaltic pumps with constituents in a sample under specific
tubings (drain and solvent addition conditions, i.e. specified solvent and endpoint.
pumps) (30094237)
 Burette DV1010 10 mL (51107501) The sample is titrated using an EQP method
 DGi113-SC, Combined pH glass function. If no inflection point is detected,
electrode (51109502) endpoints are taken at potential readings
 Compact stirrer (51109150) corresponding to those found for aqueous acidic
 LabX software and basic buffer solutions (pH 4: SAN, pH 11:
 Titration beakers PP 100 mL (101974) AN).
 3 x glass bottle (71296)
For this sample the SAN at pH 4 was not
 Spatula / Syringe
calculated, since the initial potential was already
below buffer potential 1 (pH 4).

The blank is determined by titrating the solvent SmartSample weighing is highly recommended if
mixture to buffer potential of pH 11 (B[ASTM many samples are being titrated since the error
D664 EP]). Sometimes an EQP titration would free weight and sample ID transfer from the
detect no EQP or an arbitrary EQP. This may lead XPE205 balance to the InMotion sample changer
to too large blank values. Therefore two blank contributes a lot to data integrity and security.
values can be selected. For this application
Waste disposal and safety measures
B[ASTM D664 EP] was applied:
Dispose as aromatic organic solvent (toluene)
and halogenated organic solvent (CHCl3).
References
ASTM D664-11a: Standard test method for acid
number of petroleum products by potentiometric
The rinsing procedure of the non-aqueous pH- titration.
sensor should not be shortened. If it is shortened
a decreased life time of the sensor as well as Further information
worse repeatability has to be expected. http://www.mt.com/global/en/home/products/Labo
Some oils will not show an EQP at all (i.e. a very ratory_Analytics_Browse/Product_Family_Browse_
flat curve). In these cases only the evaluation at titrators_main/Titration_Excellence.html
the buffer potentials of pH 4 and 11 can be
performed.
Measured values

Volume dV/dt Potential 1st deriv. Time Temperature
[mL] [mL/s] [mV] [mV/mL] [s] [°C]
0 70.5 0 21.8
0.005 0.0015 71.1 3 21.8
0.01 0.0015 71.3 6 21.8
0.0225 0.0035 68.8 10 21.8
0.0305 0.0025 66.3 13 21.8
0.0505 0.003 54 -507.49 20 21.8
0.0605 0.0025 49.1 -512 24 21.8
1.2345 0.0025 -219.2 -467.14 178 21.4

1.2395 0.0015 -220.2 -487.76 181 21.4
1.252 0.002 -227.5 -498.7 187 21.4
1.2585 0.002 -228.7 -496.83 190 21.4
1.268683 -235.3 EQP
1.2745 0.002 -239.1 -487.67 198 21.4
1.2795 0.002 -240 -486.79 201 21.4
1.292 0.002 -247.3 -476.12 208 21.4
1.2985 0.0025 -248.6 -476.28 210 21.5
1.3145 0.002 -257.7 218 21.4
1.322 0.002 -259.6 222 21.5
1.341 0.002 -269.2 231 21.4
1.353 0.002 -273.7 237 21.5
1.383 0.0025 -284.6 248 21.5

Type pH
Method Sensor DGi113-SC
Unit mV
001 Title
Temperature acquisition
Type General titration Temperature measurement Yes
Compatible with T9/T90 Temperature sensor DT1000
ID M726 Unit °C
Title Automated Acid Number Stir
Determintion according Speed 30 %
to ASTM D664 Predispense
Author PredefinedUser Mode None
Date/Time 07/01/2014 09:20:41 Wait time 0s
am Control
Modified on 07/03/2014 02:58:14 Control Normal
pm Mode Acid/base
Modified by PredefinedUser Titrant addition Dynamic
Protect No dE (set value) 12.0 mV
SOP None dV (min) 0.005 mL
dV (max) 0.5 mL
002 Sample Mode Equilibrium controlled
dE 0.5 mV
Number of IDs 1
dt 1s
ID 1 Oil
t (min) 3s
Entry type Weight
t (max) 30 s
Lower limit 1g
Evaluation and recognition
Upper limit 10 g
Procedure Standard
Density 1.0 g/mL
Threshold 200 mV/mL
Correction factor 1.0
Tendency Negative
Temperature 25.0°C
Ranges 1
Entry Arbitrary
Lower limit 1 -300 mV
InMotion reader SmartSample
Lower limit 2 -100 mV
Add. EQP criteria No
003 Titration stand (InMotion T/Tower A) Termination
Type InMotion T/Tower A At Vmax 10 mL
Titration stand InMotion T/2A At potential -310 mV
Lid Handling Yes Termination tendency None
At slope No
004 Pump After number of recognized EQPs No
Combined termination criteria No
Auxiliary reagent ASTM D664 Solvent Accompanying stating
Volume 40 mL Accompanying stating No
Condition No Condition
Condition No
005 Stir
Speed 35 % 008 Calculation R1
Duration 60 s Result Consumption EQP
Condition No Result unit mmol
Formula R1 = Q
006 Measure (normal) [1] Constant C=1
Sensor M M[None]
Type pH z z[None]
Sensor DGi113-SC Decimal places 3
Unit pH Result limits No
Temperature acquisition Record statistics Yes
Temperature measurement Yes Extra statistical func. No
Temperature sensor DT1000 Send to buffer None
Unit °C Write to RFID None
Stir Condition No
Speed 30 %
Acquisition of the measured values 009 Calculation R2
Acquisition Equilibrium controled Result TAN EQP
dE 0.5 mV Result unit mg KOH/g
dt 1s Formula R2 = (R1-B[ASTM D664
t (min) 3s EP]*C/m)
t (max) 30 s Constant C = M/z
Mean value No M M[Potassium hydroxide]
Condition z z[Potassium hydroxide]
Condition No Decimal places 3
Result limits No
007 Titration (EQP) [1] Record statistics Yes
Titrant Extra statistical func. No
Titrant KOH in 2-Propanol Send to buffer None
Concentration 0.1 mol/L Write to RFID None
Sensor Condition No

M M[None]
010 Calculation R3 z z[None]
Decimal places 3
Result Consumption BP
Result limits No
Result unit mmol
Record statistics Yes
Formula R3 = QE(H[Buffer
Extra statistical func. No
pH11])
Send to buffer None
Constant C=1
Write to RFID None
M M[None]
Condition No
z z[None]
Decimal places 3
Result limits No
015 Record
Record statistics Yes Summary No
Extra statistical func. No Results Per sample
Send to buffer None Raw results Per sample
Write to RFID None Table of meas. Values No
Condition No Sample data No
Resource data No
011 Calculation R4 E–V No
dE/dV – V No
Result TAN BP
log dE/dV –V No
Result unit mg KOH/g
d2E/dV2 – V No
Formula R4 = (R3-B[ASTM D664
BETA – V No
EP]*C/m
E–t No
Constant C = M/z
V–t No
M M[Potassium hydroxide]
dV/dt – t No
z z[Potassium hydroxide]
T-t No
Decimal places 3
E – V & dE/dV – V No
Result limits No
V – t & dV/dt – t No
Method No
Series data No
Send to buffer None
Condition No
Write to RFID None
Condition No
016 Drain
012 Calculation R5 Drain pump DRAIN
Drain volume 100 mL
Result Consumption SAN BP
Pump property 1-way
Result unit mmol
Condition No
Formula R5 = QE(H[Buffer pH4]
Constant C=1
M M[None]
017 Conditioning
z z[None] Interval 1
Decimal places 3 Position Conditioning beaker
Result limits No Time 90 s
Record statistics Yes Speed 30 %
Extra statistical func. No Lid Handling No
Send to buffer None Condition No
Write to RFID None
Condition Yes 018 Conditioning
Formula E<4
Interval 1
Position Special beaker 1
013 Calculation R6 Time 180 s
Result SAN BP Speed 30 %
Result unit mg KOH/g Lid Handling No
Formula R6 = (R5+B[ASTM Condition No
D664 EP]*C/m
Constant C = M/z 019 Conditioning
Interval 1
z z[Potassium hydroxide]
Decimal places 3
Time 90 s
Result limits No
Speed 30 %
Lid Handling No
Condition No
Send to buffer None
Write to RFID None
Condition Yes 020 Rinse
Formula E<4 Auxiliary reagent Water
Rinse cycles 3
014 Calculation R7 Vol. per cycle 20 mL
Position Rinse beaker
Result Initial pH
Drain Yes
Result unit pH
Drain pump DRAIN
Formula R7 = E
Condition No
Constant C=1
021 Conditioning

Interval 1
Time 500 s
Speed 30 %
Lid Handling No
Condition No
022 Conditioning
Interval 1
Position Conditioning beaker
Time 90 s
Speed 30 %
Lid Handling No
Condition No
023 End of sample
024 Park
Titration stand InMotion T/2A
Condition No


M721 – Acid Number Thermometric, ASTM D8045
Acid Number in Crude Oil by Thermometric

Titration According to ASTM D8045-2016
paraformaldehyde plays the role of thermometric

Introduction
indicator.
The monitoring of oil aging by measuring Acid
Sample preparation and procedures
Number (AN) is important for oil industry to
prevent machine breakdowns or pipelines leakage 1. Measure the Titer and the Blank following
due to corrosive acidic oil. The standard method M723 (T7 and T9) or M725 (T5)
potentiometric acid/base titration works well for 2. Depending on the AN of the sample, different
the determination of AN, but is a time consuming sample amounts are requested:
and delicate procedure. One approach to avoid
such pitfalls is to measure the temperature change Acid number Sample size
that occurs during the titration. This so called [mg KOH/g] [g]
thermometric titration is faster, needs less 0.05 – 1.0 10 +/- 1.0 - 20.0 +/- 2.0
maintenance and care of the sensor but is as 1.0 – 5.0 5.0 +/- 0.5
precise and reliable as the potentiometric 5.0 – 20.0 1.0 +/- 0.1
determination of AN.
This note describes the thermometric determin- 3. Weigh the sample in one beaker and place it
ation of the Acid Number in crude oil and other on the sample changer
petroleum products. AN is the amount of KOH 4. 30 mL of the solvent mixture (xylenes:2-
necessary to neutralize 1 g of sample, expressed propanol 75:25) containing a suspension of
as mg KOH/g. 17 g/L paraformaldehyde is automatically
added to the sample. To ensure a good
The thermometric titration of AN in oil allows a
dispersion of the paraformaldehyde in the
rapid, accurate and fully automated analysis. The
solvent, it is stirred continuously on a stirring
titration is performed with KOH in 2-propanol to a
plate.
catalyzed endpoint. A mixture of xylene and 2-
propanol (75:25) is used as solvent and

5. After each sample, the Thermotrode is Remarks
conditioned in the solvent mixture for 30 sec
A thermometric titration follows the enthalpy
in order to clean it.
change in the course of a titration by measuring
Chemistry the small difference in temperature induced by the
chemical reactions.
HA + KOH → A- + K+ + H2O
HA: Acid components In the case of thermometric acid number deter-
mination, a thermometric indicator, para-
Solutions
formaldehyde, is used to detect the titration
Titrant: Potassium hydroxide in 2-Porpanol, KOH, endpoint. Once all acid have been neutralized by
c(KOH) = 0.1 mol/L KOH, the excess of KOH produces an endothermic
Chemicals:
depolymerization of paraformaldehyde. The
Solvent: 30 mL Xylenes:2-Propanol (75:25)
sudden temperature drop indicates the endpoint of
Thermometric indicator: Paraformaldehyde 17 g/L
the titration according to the following reaction:
Compound:
AN as mg KOH/g, M = 56.11 g/mol, z = 1
Standard: Benzoic acid, M = 122.12 g/mol z=1
(see methods M723 or M725) -
+ OH +H O
Instruments and accessories 2
 Titration Excellence T5 (30252672) T7

(30252675) or T9 (30252676) The titration EQP is found using a segmented
 Conductivity board (51109840) with FW evaluation (second derivative of the curve)
version 1.5 or higher In the Titration (Therm.) method function, a
 Thermotrode (30322061) constant dosing rate of 2 mL/min should be set
 XP205 Analytical balance (11106027) for optimal results. A dynamic addition would lead
 Burette DV1010 10 mL (51107501) to unwanted temperature variations.
 Compact Stirrer (51109150)
 InMotion Flex 100 mL (30094120) The maximal volume of a thermometric titration is
 Titration beakers PP 100 mL (101974) defined by the burette volume.
 SP280 persistaltic pump (30094237)
Suspending the measurement during titration may
 Stirring plate
produce invalid results because the temperature of
 Spatula/Syringe
the solvent will equilibrate with the room
Results temperature which modifies the titration curve.
Sample mass R2: AN This application does not replace the ASTM
[g] [mg KOH/g] standard
1 5.141 1.890 The application method has been developed to be
2 5.096 1.943 used with an InMotion™ Autosampler with
3 5.035 1.930 automatic addition of solvent in the beaker.
4 4.967 1.826 However, the solvent and paraformaldehyde can
5 5.006 1.834 be added manually prior to the titration and the
6 5.014 1.812 titration can be performed on a manual titration
7 4.587 1.888 stand.
Mean 1.875
s 0.052
The Thermotrode is connected to the conductivity
srel 2.763 %
plug on a conductivity board.
The measurements were performed on motor oil.
The reproducibility of the results is good.

Waste disposal and safety measures Further information

Dispose as aromatic organic solvent http://www.mt.com/global/en/home/perm-
lp/product-organizations/ana/ThermoTAN.html
Use safety goggles, a lab coat and wear gloves. If
possible, work in a fume hood.
ASTM D8045, see www.astm.org
Paraformaldehyde is a carcinogenic powder; wear
a protecting mask during its manipulation.
Measured values
Thermometric acid number, sample 2/7
Volume Meas. value Change 2nd deriv. Time

2
[mL] [°C] [°C] [°C/mL ] [s]
0.027 23.8857 0.8
0.054 23.8831 -0.0026 1.6
0.0805 23.8766 -0.0065 2.4
0.111 23.8682 -0.0084 3.3
0.138 23.8608 -0.0074 4.1
0.165 23.8532 -0.0076 4.9
0.1915 23.8452 -0.008 5.7
0.2185 23.8372 -0.008 0.43 6.5
0.242 23.8306 -0.0066 0.27 7.2
0.269 23.8233 -0.0073 0.23 8
0.2995 23.8161 -0.0072 0.13 8.9
0.326 23.8085 -0.0076 -0.04 9.7
… … … … …
1.6445 23.4727 -0.58 48.9
1.668 23.466 -0.0067 -0.57 49.6
1.695 23.457 -0.009 -0.61 50.4
1.7255 23.4477 -0.0093 -0.52 51.3
1.7525 23.4381 -0.0096 -0.57 52.1
1.779 23.4283 -0.0098 -0.88 52.9
1.79678 23.4213 -0.007 -1.13 EQP
1.806 23.4176 -0.0037 -1.04 53.7
1.833 23.4097 -0.0079 -1.01 54.5

007 Calculation R1
Method Result Consumption
Result unit mL
001 Title
Formula R1=VEQ
Type General titration Constant C=1
Compatible with T5/T7/T9 M M[Potassium hydroxide]
ID M721 z z[Potassium hydroxide]
Title Acid Number Decimal places 3
Thermometri Result limits No
... Record statistics Yes
002 Sample Send to buffer No
Number of IDs 1 Write to Smart Tag None
ID 1 Oil Condition No
Entry type weight
Lower limit 0.0 g 008 Calculation R2
Upper limit 10 g Result Acid Number
Density 1.0 g/mL Result unit mg KOH/g
Number of sample factors 0 Formula R2=Q*C/m
Correction factor 1.0 Constant C=M/z
Temperature 25.0°C M M[Potassium hydroxide]
Entry Arbitrary z z[Potassium hydroxide]
InMotion reader None Decimal places 3
Result limits No
003 Titration stand Record statistics Yes
Type InMotion T/Tower A Extra statistical functions No
Titration stand InMotion T/1A Send to buffer No
Head position sample Write to Smart Tag None
Lid handling No Condition No
004 Pump 009 Conditioning

Auxiliary reagent Solvent Interval 1
Volume 30 mL Position Conditioning beaker
Pump property 1-way Time 30 s
Condition No Speed 30 %
Lid handling No
Condition No
005 Stir
Speed 50 %
010 End of sample
Duration 30 s
Condition No
011 Record
006 Titration (Therm.) [1] Summary Yes
Titrant Results No
Titrant KOH in 2-Propanol Raw results No
Concentration 0.1 mol/L Resource data No
Sensor Calibration curve No
Type Thermometric Method No
Sensor Thermotrode Series data No
Unit °C Condition No
Stir
Speed 50%
Control
Dosing rate 2 mL/min
Evaluation and Recognition
Procedure Segmented
Threshold 3.0 °C/mL2
Tendency None
Ranges 0
Termination
At Vmax 4 mL
After number of recognized EQPs Yes
Number of EQPs 1
Conditon
Condition No

M723 – Acid Number Thermometric, Titer and Blank
Acid Number in Crude Oil by Thermometric

Titration (ASTM D8045-2016): Titer and
Blank
1 g of sample, expressed as mg KOH/g.

Introduction
The thermometric titration of AN in oil allows a
The monitoring of oil aging by measuring Acid
rapid, accurate and fully automated analysis. The
Number (AN) is important for oil industry to
titration is performed with KOH in 2-propanol to a
prevent machine breakdowns or pipelines leakage
catalyzed endpoint. A mixture of xylene and 2-
due to corrosive acidic oil. The standard
propanol (75:25) is used as solvent and
potentiometric acid/base titration works well for
paraformaldehyde plays the role of thermometric
the determination of AN, but is a time consuming
indicator.
and delicate procedure. One approach to avoid
such pitfalls is to measure the temperature change Sample preparation and procedures
that occurs during the titration. This so called
1. Prepare a standard solution of ca. 200 mg
thermometric titration is faster, needs less
benzoic acid in ca. 80 g of 2-propanol (AN =
maintenance and care of the sensor but is as
1.15).
precise and reliable as the potentiometric
2. Write the concentration of benzoic acid in
determination of AN.
mg/g as correction factor in the sample
This note describes the thermometric determin- method function.
ation of the titer and the blank value for the Acid 3. Prepare 4 samples with ca. 2, 3, 4 and 5 g
Number in crude oil and other petroleum products. of the benzoic acid solution and place them
AN is the amount of KOH necessary to neutralize on the sample changer.
4. 30 mL of the solvent mixture (xylenes:2-

propanol 75:25) containing a suspension of
Results
17 g/L paraformaldehyde is automatically
added to the sample prior to the titration. To Sample mass R1: Consumption
ensure a good dispersion of the [g] [mL]
paraformaldehyde in the solvent, it is stirred 1 1.872 0.423
continuously on a stirring plate. 2 3.010 0.631
5. After each sample, the Thermotrode is 3 4.113 0.843
conditioned in the solvent mixture for 30 sec 4 5.123 1.028
in order to clean it.
Chemistry R5: Titer 1.003

R6: Blank [mL] 0.0722
HA + KOH → A- + K+ + H2O
R7: Final Slope [mL/g] 0.187
HA: Acid components 2
R8: R 1.000
Solutions The measurements show a good linearity. The
Titrant: Potassium hydroxide in 2-Porpanol, KOH, blank value is lower than the requested maximal
c(KOH) = 0.1 mol/L value of 0.1 mL.
Chemicals:
Remarks
Solvent: 30 mL Xylenes:2-Propanol (75:25)
Thermometric indicator:Paraformaldehyde 17 g/L A thermometric titration follows the enthalpy
Compound: change in the course of a titration by measuring
AN as mg KOH/g, M = 56.11 g/mol, z = 1 the small difference in temperature induced by the
Standard: Benzoic acid, M = 122.12 g/mol z=1 chemical reactions.
Instruments and accessories
-
 Titration Excellence T7 (30252675) or T9
+ OH +H O
(30252676) 2
 Conductivity board (51109840) with FW

version 1.5 or higher In the case of thermometric acid number deter-
 Thermotrode (30322061) mination, a thermometric indicator, para-
 XP205 Analytical balance (11106027) formaldehyde, is used to detect the titration
 Burette DV1010 10 mL (51107501) endpoint. Once all acid have been neutralized by
KOH, the excess of KOH produces an endothermic
 InMotion Flex 100 mL (30094120)
depolymerization of paraformaldehyde. The
 Titration beakers PP 100 mL (101974)
sudden temperature drop indicates the endpoint of
 SP280 persistaltic pump (30094237)
the titration according to the following reaction:
 Stirring plate
 Spatula/Syringe The titration EQP is found using a segmented
evaluation (second derivative of the curve)
In the Titration (Therm.) method function, a

constant dosing rate of 2 mL/min should be set
for optimal results. A dynamic addition would lead
to unwanted temperature variations.
The maximal volume of a thermometric titration is

defined by the burette volume.


𝑧
temperature which modifies the titration curve. R3= *(𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗ 𝑝𝑤(𝑛 −
H[slope]*c*C
Titer and blank measurement: 𝑛𝑇𝑂𝑇) ∗ 𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗ 𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗

𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗ 𝑛)
With
C=M/f
The part of the calculation with “pw(n-nTOT)”

makes the TITER ≈ 0 for all the samples except
the last one. Then in the method function TITER,
the mean of R3 is calculated, which is equal to
the last result of R3 only.
The blank value, is calculated as follow:

H[sum cont] H[sum m]
R6= − (H[slope]* )
𝑛𝑇𝑂𝑇 𝑛𝑇𝑂𝑇
The titer and blank are calculated from a linear Finally, the correlation coefficient R2 is calculated
regression of at least 3 samples of increasing as follow:
size: H[sum m]*H[sum cont] 2
(H[sum m*cont] − )
𝑛𝑇𝑂𝑇
R8=
 The titer is directly proportional to the slope of (H[sum m2 ] −
H[sum m]2
) ∗ (H[sum cont 2 ] −
H[sum cont]2
)
the linear regression
 The blank is equal to the intercept of the This application does not replace the ASTM
straight with the y-axis standard
The method generates the linear regression using
The application method has been developed to be
5 auxiliary values in which the following sums are
used with an InMotion™ Autosampler with
calculated:
automatic addition of solvent in the beaker.
 Sum of masses m (H[sum m]) However, the solvent and paraformaldehyde can
 Sum of consumptions cont (H[sum cont]) be added manually prior to the titration and the
 Sum of the masses times the consumptions titration can be performed on a manual titration
(H[sum m*cont])
stand.
 Sum of the square of the masses (H[sum
m2]) The Thermotrode is connected to the conductivity
 Sum of the square of the consumptions plug on a conductivity board.
(H[sum cont2])
All the auxiliary values are set to 0 at the
beginning of a measurement series. Dispose as aromatic organic solvent
The slope of the linear regression is calculated as Use safety goggles, a lab coat and wear gloves. If
follow: possible, work in a fume hood.
H[sum m]*H[sum cont] Paraformaldehyde is a carcinogenic powder; wear
H[sum m*cont] −
R2 = 𝑛𝑇𝑂𝑇 a protecting mask during its manipulation.
𝐻[𝑠𝑢𝑚 𝑚]2
H[sum 𝑚2 ] −
𝑛𝑇𝑂𝑇 Further information
Where nTOT is the total number of samples in the http://www.mt.com/global/en/home/perm-
series. The slope is then stored as the auxiliary lp/product-organizations/ana/ThermoTAN.html
value H[slope] ASTM D8045, see www.astm.org
As the slope is given in mL/g, to obtain a TITER
value one has to apply the following calculation:

Measured values
Thermometric acid number, sample 1/4
Volume Meas. value Change 2nd deriv. Time

2
[mL] [°C] [°C] [°C/mL ] [s]
0.0065 22.4903 NaN NaN 0.2
0.0335 22.4924 0.0021 NaN 1
0.06 22.4919 -0.0005 NaN 1.8
0.0835 22.4911 -0.0008 NaN 2.5
0.1135 22.4898 -0.0013 NaN 3.4
0.14 22.4886 -0.0012 NaN 4.2
0.1665 22.4886 0 NaN 5
0.1935 22.4867 -0.0019 0.24 5.8
0.22 22.4861 -0.0006 0.09 6.6
0.2465 22.4855 -0.0006 -0.02 7.4
0.27 22.4847 -0.0008 -0.1 8.1
0.2965 22.484 -0.0007 -0.05 9
0.3265 22.483 -0.001 -1.25 9.8
0.3535 22.4813 -0.0017 -4.44 10.6
0.38 22.4796 -0.0017 -9.13 11.4
0.4065 22.4756 -0.004 -13.17 12.2
0.423026 22.4624 NaN -15.7 EQP
0.4335 22.4541 -0.0215 -14.65 13
0.4565 22.4169 -0.0372 -13.8 13.7
0.4835 22.3666 -0.0503 -9.61 14.5
0.5135 22.3168 -0.0498 -2.89 15.4
0.54 22.2683 -0.0485 2.97 16.2
0.5665 22.2241 -0.0442 5.8 17
0.5935 22.1822 -0.0419 5.28 17.8
0.62 22.1436 -0.0386 NaN 18.6
0.6465 22.1071 -0.0365 NaN 19.4
0.67 22.0769 -0.0302 NaN 20.1

Head position sample

Method Lid handling No
010 Pump
Auxiliary reagent Solvent
001 Title Volume 30 mL
Type Titer determination Pump property 1-way
Compatible with T7/T9 Condition No
ID M723
Title M723 011 Stir
...
Speed 50 %
Duration 30 s
002 Auxiliary value Condition No
Name sum m
Formula H=0 012 Titration (Therm.) [1]
Limits No Titrant
Condition No Titrant KOH in 2-Propanol
Concentration 0.1 mol/L
003 Auxiliary value Sensor
Type Thermometric
Name sum m2 Sensor Thermotrode
Formula H=0 Unit °C
Limits No
Stir
Condition No Speed 50%
Control
004 Auxiliary value Dosing rate 2 mL/min
Name sum cont
Procedure Segmented
Formula H=0
Threshold 3.0 °C/mL2
Limits No
Tendency None
Condition No
Ranges 0
005 Auxiliary value Termination
At Vmax 4 mL
Name sum cont2
Formula H=0
Number of EQPs 1
Limits No
Conditon
Condition No
Condition No
006 Auxiliary value 013 Auxiliary value

Name sum m*cont Name sum m
Formula H=0 Formula H=m+H[sum m]
Limits No Limits No
Condition No Condition No
007 Auxiliary value 014 Auxiliary value

Name slope Name sum m2
Formula H=0 Formula H=sq(m)+H[sum m2]
Limits No Limits No
Condition No Condition No
008 Sample (Titer) 015 Auxiliary value

Name sum cont
Titrant KOH in 2-Propanol
Formula H=VEQ+H[sum cont]
Limits No
Standard Benzoic acid liq
Condition No
Type of standard Liquid
Entry type Weight
Lower limit 0.0 g 016 Auxiliary value
Upper limit 10 g Name sum m*cont
Correction factor 2.5 Formula H=m*VEQ+H[sum m
Temperature 25.0 °C *cont]
Entry Arbitrary Limits No
InMotion reader None Condition No
009 Titration stand 017 Auxiliary value

Type InMotion T/Tower A Name sum cont2
Titration stand InMotion T/1A Formula H=sq(VEQ)+H[sum

cont2] M M[Potassium hydroxide]
Limits No z z[Potassium hydroxide]
Result limits No
018 Calculation R1 Record statistics Yes
Extra statistical functions No
Result Consumption
Send to buffer No
Result unit mL
Write to Smart Tag None
Formula R1=VEQ
Condition No
Constant C=1
z z[Potassium hydroxide] 023 Conditioning
Decimal places 3 Interval 1
Result limits No Position Conditioning beaker
Record statistics Yes Time 30 s
Extra statistical func. No Speed 30 %
Send to buffer No Lid handling No
Write to Smart Tag None Condition No
Condition No
024 End of sample

019 Calculation R2
Result Slope
Result unit mL/g 025 Titer
Formula R2=(H[sum m*cont]- Titrant KOH in 2-Propanol
(H[sum m]*H[sum Concentration 0.1 mol/L
cont])/nTOT)/(H[sum TITER= Mean[R3]
m2]-(H[sum m]*H[sum Limits No
m])/nTOT) Condition No
Constant C=1
M M[None]
z z[None]
026 Calculation R5
Decimal places 4 Result Titer
Result limits No Result unit
Record statistics Yes Formula R5=Mean[R3]
Extra statistical functions No Constant C=1
Send to buffer No M M[None]
Write to Smart Tag None z z[None]
Result limits No
020 Auxiliary value Send to buffer No
Name slope Write to Smart Tag None
Formula H=R2 Condition No
Limits No
Condition No 027 Calculation R6
Result Blank value
021 Calculation R3 Result unit mL
Result Titer Formula R6=H[sum cont]/nTOT-
Result unit (H[slope]*H[sum m]
Formula R3=z/(H[slope]*c*C)* /nTOT)
pw(n-nTOT)*pw(n- Constant C=1
nTOT) M M[None]
*pw(n-nTOT)*pw(n- z z[None]
nTOT)*pw(n-nTOT)*n Decimal places 4
Constant C=M/f Result limits No
M M[Benzoic acid liq] Record statistics Yes
z z[Benzoic acid liq] Send to buffer No
Decimal places 3 Write to Smart Tag None
Result limits No Condition No
Extra statistical functions No 028 Blank
Send to buffer No
Name Solvent FFA
Value B= R6
Condition No
Unit mL
Limits No
022 Calculation R4 Condition No
Result Content
Formula R4=Q*C/m
029 Calculation R7
Constant C=M/z Result Final Slope

Result unit mL/g

Formula R7=H[slope]
Constant C=1
M M[None]
z z[None]
Decimal places 3
Result limits No
Send to buffer No
Condition No
030 Calculation R8
Result R8
Result unit
Formula R8=(sq(H[sum
m*cont]-
(H[sum m]*H[sum
cont]
)/nTOT))/((H[sum m2]-
sq(H[sum m])/nTOT)*
(H[sum cont2]-sq(
H[sum cont])/nTOT))
Constant C=1
M M[None]
z z[None]
Decimal places 3
Result limits No
Send to buffer No
Condition No
031 Record
Summary Yes
Results No
Raw results No
Resource data No
Calibration curve No
Method No
Series data No
Condition No

Base Number Determination
Base Number Determination
Basic additives are used in oils to neutralize the formation of acidic compound during the oil’s life. A monitoring
of the amount of these basic additives, the Base Number (BN), is important to prevent the formation of corrosive
acidic oil and to plan oil replacement efficiently.
Base Number is usually titrated potentiometrically by an acid in a non-aqueous medium and is expressed as
the amount of equivalent base present per gram sample, given as mg KOH/g.
All the existing standards on Base Number determination describe potentiometric non-aqueous acid-base
titrations using different titrants such as perchloric acid or hydrochloric acid (see Table 2). As for the Acid
Number determination, the pH electrode has to be thoroughly cleaned and well-conditioned after every sample
measurement to ensure repeatable results and a good working electrode, which takes a lot of time.
Thermometric titration works also well for Base Number determination. It is a fast technique and does not
require long conditioning and cleaning of the thermotrode.
Three Base Number methods are presented in this application brochure:
 The potentiometric method M696, according to ASTM D4739
 The thermometric method M693
 The thermometric method M694 for blank and titer determination
Standard Description of test Mettler-Toledo Titration methods

ASTM D2896 Base Number by Perchloric Acid Titration M430
ASTM D4739 Base Number by Hydrochloric Acid Titration M364, M696
ASTM D974 Base Number by Color Indicator Titration
DIN ISO 3771 Base Number by Hydrochloric Acid Titration
IP 139 Base Number by Color Indicator Titration
IP 276 Base Number by Perchloric Acid Titration
IP 417 Base Number by Potentiometric HCl Titration
Base Number by thermometric titration M693, M694
Table 2: Standards for the determination of Base Number

M696 – Base Number according to ASTM D4739
Automated Base Number Determination

according to ASTM D4739
Base number is the amount of equivalent

Introduction
potassium hydroxide contained per gram sample,
The determination of the base number plays a expressed as mg KOH/g.
significant role in the quality control of petroleum
products to estimate the amount of additive
depletion, acidic contamination and oxidation. 1. Titer determination of KOH in 2-propanol: add
The base number is a measure of the amount of ~ 100 mg KHP into a titration beaker with
basic substances in oil under the conditions of the 60 mL deionized water.
test. 2. Titer determination of HCl: Add 8.0 mL of
KOH in 2-propanol into titration beaker with
New and used petroleum products can contain
40 mL 2-propanol.
basic constituents that are present as additives.
3. The buffer potentials (at pH 3) are saved as
The relative amount of these substances can be
auxiliary values
determined by titration with acids. It is sometimes
4. A new blank value is determined and stored
used as a measure of oil degradation in service,
for every new batch of solvent mixture.
by comparison with an empirically established
5. Rinse beaker and a two conditioning beaker
limit.
(water and solvent) on the InMotion Max
This note describes the potentiometric deter- (100 mL beakers) have been used for rinsing
mination of the base number (BN) in a motor oil and regenerating the DGi116-SC electrode.
sample according to ASTM D4739.

6. Conditioning beakers:  Burette DV1010 10 mL (51107501)
7. Water and ASTM D4739 solvent  Burette DV1020 20 mL (51107502)
8. Rinse beaker: Power shower rinsing with 2-  Dosing unit (51109030)
propanol (SD660)  DGi116-Solvent, Combined pH glass
9. The optimal rinsing sequence for this electrode (51109502)
 Compact stirrer (51109150)
application is the following:
 Conditioning in conditioning beaker for 300 s  LabX® software
 Rinsing with 2-propanol in rinse beaker  Titration beakers PP 100 mL (101974)
 Conditioning in conditioning beaker for 10 s  3 x glass bottle (71296)
 Titration of sample  Spatula / Syringe
 Rinsing with 2-propanol- conditioning for Results
30 s.
 Park in conditioning beaker
10. Weigh appropriate amount of sample and R1: BN EQP R2: BN BP
place the beaker in InMotion rack. [mg KOH/g] [mg KOH/g]
11. 60 mL of ASTM solvent are automatically 1 9.59 8.87
added using an additional dosing unit. 2 9.53 8.84
12. At the end of the titration, the beaker is 3 9.59 8.84
automatically drained using an SP280 4 9.53 8.83
peristaltic pump. 5 9.73 9.02
6 9.56 8.86
Chemistry
Mean 9.59 8.88
HCl + BOH = BCl + H2O s 0.07 0.07
BOH: Base components srel 0.776 % 0.808 %
Solutions
The titration curve of the motor oil sample was
Titrant: Hydrochloric acid in 2-Propanol found to be flat, EQP detection was challenging.
HCl, c(HCl) = 0.1 mol/L The base number was therefore determined by
Chemicals: 60 ml ASTM D4739 solvent: titrating the sample to buffer potential of pH 3
Toluene : Chloroform : 2-Propanol : H2O H[Buffer pH3].
1 L : 1 L : 1 L : 30 mL)
2-Propanol for rinsing Remarks
Standard: Potassium hydrogen phthalate KHP
Depending on the BN of the sample, a sample
Potassium hydroxide in 2-Propanol KOH,
size of 0.1 g to 5 g is recommended.
c(KOH) = 0.1 mol/L
Compound: BN as mg KOH/g, Potassium The sample size used for this analysis was ~1 g
hydroxide, M = 56.11 g/mol, z = 1 of motor oil.
Instruments and accessories Perform a blank titration of the same volume of
 Titration Excellence T7 (30252675) or T9 titration solvent used for the sample. The blank of
(30252676) the solvent has to be determined regularly, at least
 XPE205 Analytical balance (30087653) after preparing a new stock of solvent mixture.
 InMotion™ Max Base (30094122) The blank is determined by titrating the solvent
 InMotion™ Max Rack Kit 100 mL mixture to buffer potential up to pH 3 and is saved
(30094131)
as B[ASTM D4739 EP].
 SD660 membrane pump for power shower
rinsing (included in InMotion™ Max Base The sample is titrated using an EQP method
delivery) function. If no EQP is detected, than evaluation of
 SP280 peristaltic pumps with tubings (drain the BN is made to the acidic buffer potential (pH 3
pump) (30094237) buffer). The buffer potential determination has to
be carried out every day after the calibration of the Waste disposal
electrode, or when using a different electrode.
Dispose as halogenated organic solvent
After every titration, rinsing and conditioning of (chloroform, CHCl3).
sensor should be performed properly to avoid
References
decrease in life time of sensor and bad
repeatability of results. ASTM D4739 -11: “Standard test method for base
number determination by potentiometric
Hydrochloric acid titration”.
Further information
http://www.mt.com/ch/en/home/products/Laborato
ry_Analytics_Browse/Product_Family_Browse_titra
tors_main/Titration_Excellence.html?cmp=als_Titr
ation-Excellence

Measured values
Volume Measured Value 1st deriv. EQP

[mL] [mV] [dV] [dE] [mV/mL]
0 5.3 -
0.5 139.5 0.5 134.2
0.6 142.6 0.1 3.1
0.7 148.4 0.1 5.8
0.8 151.9 0.1 3.5
0.9 155.8 0.1 3.9 20.68
1.0 158.9 0.1 3.1 33.91
1.1 162.5 0.1 3.6 45.33
1.2 167.1 0.1 4.6 57.23
1.3 175.9 0.1 8.8 104.55
1.4 191.1 0.1 15.2 209.17
1.5 209.7 0.1 18.6
1.6 236.2 0.1 26.5
1.689715 289.5 EQP
1.7 295.6 0.1 59.4
1.8 349.4 0.1 53.8
1.9 368.8 0.1 19.4


Method
Sensor
001 Title
Type pH
Type General titration Sensor DGi116-Solvent
Compatible with T5/T7/T9 Unit mV
ID M696 Temperature acquisition
Title TBN titration Temperature measurement No
… Stir
Speed 35 %
Predispense
002 Conditioning Mode Volume
Volume 0.5 mL
Titration stand InMotion T/1A Wait time 60 s
Position Conditioning beaker Control
Time 300 s Control User
Speed 30 % Titrant addition Incremental
Lid handling No dV 0.1 mL
Condition No Mode Fixed time
dt 90 s
003 Rinse Evaluation and recognition
Titration stand InMotion T/1A Procedure Standard
Auxiliary reagent 2- propanol Threshold 80.0 mV/mL
Rinse cycles 1 Tendency None
Vol. per cycle 10 mL Ranges 1
Position Rinse beaker Lower limit 1 H[Buffer pH3] mV
Drain Yes Upper limit 1 H[Buffer pH3]+100 mV
Drain pump WASTE Add. EQP criteria No
Condition No Termination
At Vmax [mL] 5.0
At potential Yes
004 Conditioning
Potential [mV] H[Buffer pH3]+140
Titration stand InMotion T/1A Termination tendency Positive
Position Conditioning beaker At slope No
Time 10 s After number of Yes
Speed 30 % recognized EQPs
Lid handling No Number of EQPs 1
Condition No Combined termination No
Criteria
005 Sample Accompanying Stating
Accompanying stating No
Number of IDs 1
Condition
ID 1 Motor Oil
Condition No
Entry type Weight
Lower limit 0.1 g
Upper limit 20 g 010 Calculation R1 (Content EQP)
Density 1.0 g/mL Result Content (EQP)
Correction factor 1.0 Result unit mg KOH/g
Temperature 25.0 °C Formula R1= (Q-B[ASTM
Entry Arbitrary D4739])*C/m
InMotion reader None Constant C= M/z
006 Titration stand (InMotion T/Tower A) z z[Potassium hydroxide]
Decimal places 2
Type InMotion T/Tower A
Result limits No
Head position Sample
Send to buffer No
Lid Handling No
Condition No
007 Dispense (normal)
Titrant ASTM D4739 011 Calculation R2 (Content Buffer potential)
Result Content (Buffer Potential)
Volume 60 mL
Dosing rate 60.0 mL/min
Formula R2= (QE(H[Buffer pH3])-
Condition No
B[ASTM D4739])*C/m
Constant C= M/z
008 Stir M M[Potassium hydroxide]
Speed 35 % z z[Potassium hydroxide]
Duration 60 s Decimal places 2
Condition No Result limits No
009 Titration EQP [1] Send to buffer No
Titrant Condition No
Titrant HCl in 2-Propanol

012 Drain
Drain pump WASTE
Drain volume 100 mL
Pump property 1-way
Condition No
013 Rinse
Auxiliary reagent 2- propanol
Rinse cycles 3
Vol. per cycle 20.0 mL
Position Rinse beaker
Drain Yes
Drain pump WASTE
Condition No
014 Conditioning
Interval 1
Time 30
Speed 30 %
Lid handling No
Condition No
015 End of sample
017 Record
Summary Yes
Results No
Raw results No
Resource data No
Method No
Series data No
Condition No
018 Park
Condition No

M693 – Base Number Thermometric
Base Number Determination in Oil by

Thermometric Titration
Introduction
2. Use the recommended sample size
Oils and lubricants usually contain basic additives depending on the BN value of the sample:
that neutralize the acid formed during the oil use.
The goal of these additives is to increase the Base Number Sample size
period of use and to prevent corrosion or machine
[mg KOH/g] [g]
breakdown. It is therefore important to know the
amount of basic additives of oils and lubricants, 0.05 – 1 10 +/- 2.0
the so-called base number.
1–5 5.0 +/- 0.5
This note describes the thermometric determin-
5 – 20 1.0 +/- 0.1
ation of the base number (BN) of oils and
lubricants. BN is the amount of equivalent 20 – 100 0.25 +/- 0.02
potassium hydroxide contained per gram sample, 100 – 250 0.1 +/- 0.01
expressed as mg KOH/g.
3. Weigh the sample in a beaker and place it on
The thermometric titration of BN allows a rapid the sample changer
and accurate analysis that can be fully 4. 30 mL of toluene is automatically added to
automatized with the InMotion™ autosampler. the sample
The titration is performed with Triflic acid or 5. During the measurement, an instruction
perchloric acid in glacial acetic acid to an window asks to add 1 mL of isobutyl vinyl
endpoint detected catalytically. Isobutyl vinyl ether ether
plays the role of thermometric indicator. 6. After each sample, the Thermotrode is rinsed
Sample preparation and procedures with toluene in order to clean it.
1. Measure the Titer and the Blank following

method M694

Chemistry Results
+ +
KOH + H → K + H2O Standard motor oil was measured. The detailed
KOH: alkaline components results are presented below
+
H : acidic titrant Sample mass R2: Base Number
[g] [mg KOH/g]
Solutions 1 1.057 8.40

2 1.028 8.64
Titrant: Trifluoromethanesulfonic acid (triflic acid, 3 1.041 8.32
CF3SO3H) = 0.1 mol/L in glacial acetic acid 4 1.035 8.43
or 5 1.006 8.63
perchloric acid (HClO4) = 0.1 mol/L in glacial 6 1.016 8.28
acetic acid 7 1.038 8.33
Chemicals: 8 1.025 8.33
Solvent: Toluene Mean 8.42
Indicator: Isobutyl vinyl ether s 0.035
Compound: BN as mg KOH/g, Potassium Srel 1.731 %
hydroxide, M = 56.11 g/mol, z = 1 The repeatability of the results is good,
Standard: Potassium hydrogen phthalate, considering the relatively high dosing rate of
M = 204.22 g/mol z=1 (see method M694) 4 mL/min needed for this titration. A slower dosing
rate could lead to an even better repeatability, but
Instruments and accessories the temperature jump at the EQP would be less
pronounced.
 Titration Excellence T5 (30252672) T7
(30252675) or T9 (30252676)
version 1.5 or higher
Remarks
 Thermotrode (30322061) A thermometric titration follows the enthalpy
 XP205 Analytical balance (11106027) change in the course of a titration by measuring
 Burette DV1010 10 mL (51107501) the small difference in temperature induced by the
 Compact Stirrer (51109150) chemical reactions.
 InMotion™ Flex 100 mL (30094120)
 SP280 peristaltic pump (30094237) Once all alkaline components are neutralized by
 SD660 membrane pump (included in triflic acid (or perchloric acid), the excess of acid
InMotion™ Flex 100 mL standard delivery) induces an exothermic polymerization of isobutyl
 Titration beakers PP 100 mL (101974) vinyl ether. The sudden temperature increase
 Rainin pipette 1 mL + pipette tips indicates the endpoint of the titration.
 Spatula/Syringe
The titration EQP is found using a segmented
evaluation (second derivative of the curve).
In the Titration (Therm.) method function, a
constant dosing rate of 4 mL/min should be set
for optimal results.
defined by the burette volume.

temperature which modifies the titration curve.

The application method has been developed for The Thermotrode is connected to the conductivity
the mentioned sample. It may be necessary to plug on a conductivity board.
optimize the method for other samples.
Waste disposal
For this application, an InMotion™ autosampler
Dispose as non-halogenated organic solvent.
with automatic addition of solvent in the beaker is
used. However, the solvent can be added Further information
manually and the titration can be performed on a
http://www.mt.com/global/en/home/perm-
manual titration stand.
lp/product-organizations/ana/ThermoTAN.html
Measured values
Thermometric titration curve and second derivative of BN in motor oil, sample 2/8

Volume Meas. value Change in Temp. 2nd deriv. Time
2
[mL] [°C] [°C] [°C/mL ] [s]
0.05375 24.1592 0.8
0.10775 24.1872 0.028 1.6
0.1615 24.2523 0.0651 2.4
0.222 24.3263 0.074 3.3
0.27575 24.4011 0.0748 4.1
0.3295 24.4798 0.0787 4.9
0.3835 24.5592 0.0794 5.7
0.43725 24.6424 0.0832 0.47 6.5
0.48425 24.7221 0.0797 0.44 7.2
0.53825 24.8123 0.0902 0.21 8
0.592 24.9004 0.0881 0.18 8.8
0.6525 24.9922 0.0918 0.11 9.7
… … … … …
1.77575 26.9275 0.0991 0.87 26.4
1.82975 27.0302 0.1027 1.83 27.3
1.89025 27.1429 0.1127 3.91 28.1
1.944 27.2577 0.1148 7.45 28.9
1.99775 27.3885 0.1308 12.39 29.7
2.04316 27.5268 0.1383 12.76 EQP
2.05175 27.553 0.0262 14.14 30.5
2.09875 27.7377 0.1847 9.92 31.2
2.1525 28.0493 0.3116 -1.37 32
2.20625 28.4131 0.3638 32.8
2.267 28.595 0.1819 33.7
2.32075 28.6086 0.0136 34.5
2.3745 28.5835 -0.0251 35.3
2.42825 28.5564 -0.0271 36.1

Termination
Method At Vmax 5 mL
Number of EQPs 1
001 Title Conditon
Type General titration Condition No
Compatible with T5/T7/T9
ID M693 008 Calculation R1
Title BN thermometric titration
Result Consumption
...
Result unit mL
Formula R1=VEQ
Constant C=1
002 Sample M M[Potassium hydroxide]
Number of IDs 1 z z[Potassium hydroxide]
ID 1 -- Decimal places 3
Entry type weight Result limits No
Lower limit 0.0 g Record statistics Yes
Upper limit 15 g Extra statistical func. No
Density 1.0 g/mL Send to buffer No
Number of sample factors 0 Write to Smart Tag None
Correction factor 1.0 Condition No
Temperature 25.0°C
Entry Arbitrary 009 Calculation R2
InMotion reader None Result BN
Formula R2=(VEQ-B[Blank TBN])
003 Titration stand *c*TITER*C/m
Type InMotion T/Tower A Constant C=M/z
Titration stand InMotion T/1A M M[Potassium hydroxide]
Head position sample z z[Potassium hydroxide]
Lid handling No Decimal places 3
Result limits No
004 Pump
Auxiliary reagent Solvent Send to buffer No
Volume 30 mL Write to Smart Tag None
Pump property 1-way Condition No
Condition No
010 Rinse
005 Instruction
Instruction Add 1 mL isobutyl vinyl Rinse cycles 2
ether Vol. per cycle 10 mL
Continue after Confirmation Position Current position
Print No Drain Yes
Drain pump SP280
006 Stir
Speed 50 % 012 End of sample
Duration 30 s
Condition No
011 Record
Summary Yes
007 Titration (Therm.) [1]
Results No
Titrant Raw results No
Titrant Triflic Acid Resource data No
Concentration 0.1 mol/L Calibration curve No
Sensor Method No
Type Thermometric Series data No
Sensor Thermotrode Condition No
Unit °C
Stir
Speed 50 %
013 Park
Control Titration stand InMotion T/1A
Dosing rate 4 mL/min Position Conditioning beaker
Procedure Segmented
Threshold 5 °C/mL2
Tendency None
Ranges 0
Add. EQP criteria Steepest jump
Steepest jumps 1


M694 – Base Number Thermometric, Blank + Titer
Base Number Determination in Oil by

Thermometric Titration: Titer and Blank
titration is performed with Triflic acid or perchloric

Introduction
acid in glacial acetic acid to an endpoint detected
Oils and lubricants usually contain basic additives catalytically. Isobutyl vinyl ether plays the role of
that neutralize the acid formed during the oil use. thermometric indicator.
The goal of these additives is to increase the
period of use and to prevent corrosion or machine
breakdown. It is therefore important to know the 1. Prepare a solution of ca. 400 mg potassium
amount of basic additives of oils and lubricants, hydrogen phthalate in ca. 100 g of glacial
the so-called base number. acetic acid
2. Write the concentration of potassium
This note describes the determination of the titer of
hydrogen phthalate in mg/g as correction
the titrant and the blank value for the thermometric
factor in the sample (Titer) method function
determination of the base number (BN) of oils and
3. Prepare 4 samples with ca. 5, 7, 9 and 11 g
lubricants. BN is the amount of equivalent
of the potassium hydrogen phthalate solution
potassium hydroxide contained per gram sample,
and place them on the sample changer
expressed as mg KOH/g. Both titer and blank
4. 30 mL of toluene is automatically added to
values are measured using a linear regression of
the sample prior to the titration
4 measurements of potassium hydrogen
5. Add 1 mL isobutyl vinyl ether when the popup
phthalate.
message appears
The thermometric titration of BN allows a rapid
and accurate analysis that can be fully
Chemistry
automatized with the InMotion™ autosampler. KOH + H+ →K+ + H2O
The KOH: alkaline components
H+: acidic titrant

Solutions A thermometric titration follows the enthalpy
change in the course of a titration by measuring
Titrant: Trifluoromethanesulfonic acid (triflic acid,
the small difference in temperature induced by the
CF3SO3H) = 0.1 mol/L in glacial acetic acid
chemical reactions.
or
perchloric acid (HClO4) = 0.1 mol/L in glacial Once all alkaline components are neutralized by
acetic acid triflic acid (or perchloric acid), the excess of acid
Chemicals: induces an exothermic polymerization of isobutyl
Solvents: Toluene, glacial acetic acid vinyl ether. The sudden temperature increase
Indicator: Isobutyl vinyl ether indicates the endpoint of the titration.
Standard: Potassium hydrogen phthalate, M =
The titration EQP is found using a segmented
204.22 g/mol z=1
evaluation (second derivative of the curve).
Instruments and accessories In the Titration (Therm.) method function, a
 Titration Excellence T5 (30252672) T7 constant dosing rate of 4 mL/min should be set
(30252675) or T9 (30252676) for optimal results.
version 1.5 or higher
 Thermotrode (30322061) defined by the burette volume.
 XP205 Analytical balance (11106027) Suspending the measurement during titration may
 Burette DV1010 10 mL (51107501) produce invalid results because the temperature of
 Compact Stirrer (51109150) the solvent will equilibrate with the room
 InMotion™ Flex 100 mL (30094120) temperature which modifies the titration curve.
 SP280 peristaltic pump (30094237)
 SD660 membrane pump (included in Titer and blank measurement:
InMotion™ Flex 100 mL standard delivery) The titer and blank are calculated from a linear
 Titration beakers PP 100 mL (101974) regression of at least 3 samples of increasing
 Rainin pipette 1 mL + pipette tips
size:
 Spatula/Syringe
The titer is directly proportional to the slope of the
linear regression
Results
The blank is equal to the intercept of the straight
Sample R2: Consumption line on the y-axis
mass [mL]
[g]
1 4.661 1.174
2 6.887 1.682
3 8.534 1.977
4 11.88 2.802
Final results
R4: Titer 0.815

R5: Blank [mL] 0.1193
R6: Final Slope [mL/g] 0.244 The method generates the linear regression using
2
R7: R 0.997 5 auxiliary values in which the following sums are
calculated:
The measurements show a good linearity.  Sum of masses m (H[sum m])
 Sum of consumptions cont (H[sum cont])
Remarks
 Sum of the masses times the consumptions The part of the calculation with “pw(n-nTOT)”
(H[sum m*cont]) makes the TITER ≈ 0 for all the samples except
 Sum of the square of the masses (H[sum the last one. Then in the method function TITER,
m2]) the mean of R3 is calculated, which is equal to
 Sum of the square of the consumption the last result of R3 only.
(H[sum cont2])
All the auxiliary values are set to 0 at the The blank value, is calculated as follow:
beginning of a measurement series.
The slope of the linear regression is calculated as H[sum cont] H[sum m]
R5= − (H[slope]* )
follow:
H[sum m]*H[sum cont] Finally, the correlation coefficient R2 is calculated

H[sum m*cont] −
R2 = 𝑛𝑇𝑂𝑇 as follow:
𝐻[𝑠𝑢𝑚 𝑚]2
H[sum 𝑚2 ] −
𝑛𝑇𝑂𝑇 H[sum m]*H[sum cont] 2
(H[sum m*cont] − )
𝑛𝑇𝑂𝑇
R7=
Where nTOT is the total number of samples in the H[sum m]2 H[sum cont]2
(H[sum m2 ] − ) ∗ (H[sum cont 2 ] − )
series. The slope is then stored as the auxiliary
value H[slope]
As the slope is given in mL/g, to obtain a TITER Waste disposal and safety measures
value one has to apply the following calculation: Dispose as non-halogenated organic solvent.
𝑧
R3= *(𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗ 𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗
H[slope]*c*C
Further information
𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗ 𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗ 𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗ 𝑛)
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With lp/product-organizations/ana/ThermoTAN.html
C=M/f
Measured values
Thermometric titration and curve of the second derivative, sample 1/4

Volume Meas. value Change in Temp 2nd deriv. Time
2
[mL] [°C] [°C] [°C/mL ] [s]
0.3835 23.7072 5.7
0.05375 23.5419 -0.1653 0.8
0.10775 23.5568 0.0149 1.6
0.1615 23.5844 0.0276 2.4
0.21525 23.614 0.0296 3.3
0.27575 23.6438 0.0298 4.1
0.3295 23.674 0.0302 4.9
0.43725 23.7425 0.0685 0.26 6.5
0.48425 23.774 0.0315 0.27 7.2
0.53825 23.8103 0.0363 0.14 8
0.592 23.8442 0.0339 0.17 8.8
0.6525 23.8819 0.0377 0.5 9.7
0.70625 23.9207 0.0388 0.81 10.5
0.76 23.9628 0.0421 0.98 11.3
0.814 24.0067 0.0439 0.93 12.1
0.861 24.0493 0.0426 0.76 12.8
0.91475 24.0956 0.0463 0.68 13.6
0.96875 24.1449 0.0493 0.83 14.4
1.02925 24.1998 0.0549 1.09 15.3
1.083 24.2575 0.0577 1.27 16.1
1.13675 24.3192 0.0617 1.52 16.9
1.1905 24.3835 0.0643 1.8 17.7
1.2445 24.4497 0.0662 2.31 18.5
1.2915 24.5126 0.0629 2.41 19.2
1.34525 24.5939 0.0813 25.66 20
1.39925 24.6876 0.0937 72.52 20.8
1.442967 24.7797 0.0921 75.01 EQP
1.45975 24.8151 0.0354 89 21.7
1.5135 25.2107 0.3956 65.11 22.5
1.56725 27.154 1.9433 13.85 23.3
1.62125 28.4337 1.2797 -44.47 24.1
1.675 28.6283 0.1946 24.9
1.722 28.6293 0.001 25.6
1.77575 28.6032 -0.0261 26.4
1.82975 28.5747 -0.0285 27.3
1.89025 28.5446 -0.0301 28.1

Lid handling No
Method
001 Title 010 Pump
Type Titer determination Auxiliary reagent Solvent
Compatible with T7/T9 Volume 30 mL
ID M694 Pump property 1-way
Title Thermometric titration of Condition No
BN Titer
...
011 Instruction
Instruction Add 1 mL isobutyl vinyl
002 Auxiliary value Ether
Name sum m Continue after Confirmation
Formula H=0 Print No
Limits No 012 Stir
Condition No
Speed 50 %
Duration 30 s
003 Auxiliary value Condition No
Name sum m2
Formula H=0 013 Titration (Therm.) [1]
Limits No Titrant
Condition No Titrant Triflic Acid
Sensor
004 Auxiliary value Type Thermometric
Name sum cont Sensor Thermotrode
Formula H=0 Unit °C
Limits No Stir
Condition No Speed 50 %
Control
005 Auxiliary value
2
Name sum cont Procedure Segmented
Formula H=0 Threshold 3.0 °C/mL2
Limits No Tendency None
Condition No Ranges 0
006 Auxiliary value Steepest jump 1
Termination
Name sum m*cont
At Vmax 4 mL
Formula H=0
Limits No
Number of EQPs 1
Condition No
Conditon
Condition No
007 Auxiliary value
Name slope 014 Auxiliary value
Formula H=0 Name sum m
Limits No Formula H=m+H[sum m]
Condition No Limits No
Condition No
008 Sample (Titer)

015 Auxiliary value
Titrant Triflic Acid
Concentration 0.1 mol/L Name sum m2
Standard Potassium Hydrogen Formula H=sq(m)+H[sum m2]
Phthalate Limits No
Type of standard Liquid Condition No
Entry type Weight
Lower limit 0.0 g 016 Auxiliary value
Upper limit 15g Name sum cont
Correction factor 4.0 Formula H=VEQ+H[sum cont]
Temperature 25.0 °C Limits No
Entry Arbitrary Condition No
InMotion reader None
017 Auxiliary value

009 Titration stand Name sum m*cont
Type InMotion T/Tower A Formula H=m*VEQ+H[sum m
Titration stand InMotion T/1A *cont]
Head position sample Limits No

Condition No
018 Auxiliary value 023 Rinse

2
Name sum cont Auxiliary reagent Solvent
Formula H=sq(VEQ)+H[sum Rinse Cycles 2
2
cont ] Vol. per cycles 10 mL
Limits No Position Current position
Condition No Drain Yes
Drain pump SP280
019 Calculation R1
Result Consumption 024 End of sample
Result unit mL
Formula R1=VEQ
Constant C=1 025 Titer
M M[Potassium hydroxide] Titrant Triflic Acid
z z[Potassium hydroxide] Concentration 0.1 mol/L
Decimal places 3 TITER= Mean[R3]
Result limits No Limits No
Record statistics Yes Condition No
Send to buffer No
026 Park
Condition No Titration stand InMotion T/1A
Position Conditioning
beaker
020 Calculation R2
Result Slope
Result unit mL/g 027 Calculation R4
Formula R2=(H[sum m*cont]- Result Titer
(H[sum m]*H[sum Result unit
cont])/nTOT)/(H[sum Formula R4=Mean[R3]
m2]-(H[sum m]*H[sum Constant C=1
m])/nTOT) M M[None]
Constant C=1 z z[None]
M M[None] Decimal places 3
z z[None] Result limits No
Decimal places 4 Record statistics Yes
Result limits No Send to buffer No
Record statistics Yes Write to Smart Tag None
Extra statistical functions No Condition No
Send to buffer No
Write to Smart Tag None 028 Calculation R5
Condition No
Result Blank value
Result unit mL
021 Auxiliary value Formula R5=H[sum cont]/nTOT-
Name slope (H[slope]*H[sum m]
Formula H=R2 /nTOT)
Limits No Constant C=1
Condition No M M[None]
z z[None]
Decimal places 4
022 Calculation R3
Result limits No
Result Titer Record statistics Yes
Result unit Send to buffer No
Formula R3=z/(H[slope]*c*C)* Write to Smart Tag None
pw(n-nTOT)*pw(n-nTOT) Condition No
*pw(n-nTOT)*pw(n-
nTOT)*pw(n-nTOT)*n
Constant C=M/f
029 Blank
M M[Potassium hydrogen Name Blank TBN
phthalate] Value B R5
z z[Potassium hydrogen Unit mL
phthalate] Limits No
Decimal places 3 Condition No
Result limits No
Record statistics Yes 030 Calculation R6
Result Final Slope
Send to buffer No
Result unit mL/g
Formula R6=H[slope]
Condition No
Constant C=1

M M[None]
z z[None]
Decimal places 3
Result limits No
Send to buffer No
Condition No
031 Calculation R7
Result R2
Result unit
Formula R7=(sq(H[sum m*cont]-
(H[sum m]*H[sum cont]
)/nTOT))/((H[sum m2]-
sq(H[sum m])/nTOT)*
(H[sum cont2]-sq(
H[sum cont])/nTOT))
Constant C=1
M M[None]
z z[None]
Decimal places 3
Result limits No
Send to buffer No
Condition No
032 Record
Summary Yes
Results No
Raw results No
Resource data No
Method No
Series data No
Condition No

Bromine Index and Bromine Number
Bromine Index and Bromine Number
Petroleum products are mixtures of different hydrocarbons, for which it is important to know more precisely the
composition. The amount of alkenes components, or in other words the degree of unsaturation of hydrocarbons
can be known by measuring its bromine index or bromine number.
Bromine reacts with the double bounds of alkenes to form brominated alkanes:
By knowing how many brome molecules react with the sample, one can know the number of double bounds it
contains. The bromine index and bromine number are given as the quantity of bromine that can react with
100 g of sample. Bromine index, which is normally lower than bromine number, is given as mg Br2 /100 g
whereas bromine number is given as g Br2 /100 g.
Bromine number is always performed volumetrically, adding a solution of Br2 to the sample, see M728
according to ASTM D1159. For the bromine index measurement, samples can be titrated volumetrically as well,
as described in the application note M597 according to ASTM D2710 or, for low bromine index, a coulometric
method can be used, see methods M716 and M717 according to ASTM D1492. For all these applications, a
polarized double platinum pins electrode DM143 is used.
In this brochure we present the following two applications:
- Low bromine index using 5 mA generating current according to ASTM D1492, application note M717
- Bromine number measurement according to ASTM D1159, application note M728.
Standard Description of test Titration method

ASTM D1159 Bromine Numbers of Distillates and Aliphatic Olefins M728
ASTM D1492 Bromine Index of Aromatic Hydrocarbons by Coulometric Titration M716, M717
ASTM D2710 Bromine Index of Hydrocarbons M597
ASTM D5776 Bromine Index of Aromatic Hydrocarbons M457
IP 130 Bromine Number of Distillates and Aliphatic Olefins
ISO 3839 Bromine Number of Distillates and Aliphatic Olefins
UOP 304 Bromine Number and Index of Hydrocarbons
Table 3: Standards for the determination of bromine index and bromine number

M717 – Bromine Index, ASTM D1492
Bromine Index Determination According to

ASTM D1492 (5 mA)

Introduction
1. Prepare a potassium bromide (KBr) solution:
Petroleum products normally consist of a mixture
Dissolve 119 g of potassium bromide (KBr)
of many different hydrocarbon molecules
in deionized water and dilute to 1 L.Prepare
containing C=C double bonds. The number of
the coulometric electrolyte without mercury
double bonds corresponds to the degree of
acetate: 600 mL glacial acetic acid, 260 mL
unsaturation. Bromine index is the analytical
of absolute methanol and 140 mL of the
procedure designed to determine the degree of
potassium bromide (KBr) solution are added
unsaturation or content of reactive C=C double
into 1 L volumetric flask.
bonds (olefins) in a hydrocarbon.
2. Standard Preparation: 200 mL toluene is
This application note describes Bromine Index (20 added to a flask. 109.6 µL cyclohexene,
– 2000 mg Br/100g) determination in a cyclo- C6H12, is added using a pipette. The
hexene standard solution by coulometric titration theoretical Br-index is 100 mg Br/100g. Keep
on Titration Excellence T5/T7/T9 according to the volumetric flask closed.
ASTM D1492-13 with a generation current of 3. Sample titration: Add 125 mL coulometric
5 mA. This standard is applied to aromatic electrolyte in a clean, dry titration cell.
hydrocarbons with traces of olefins (alkenes), 4. Start the analysis. A pretitration, a method
usually having Br- Indexes below 500. function included in the Method, is performed
before each sample in order to start from a
predefined start potential.

5. Aliquots of 0.6 g are injected into the titration
Remarks
cell using a syringe with needle. The titration
is terminated when the measured potential is Bromine index: Milligrams (mg) of bromine
below the set endpoint of 35 mV during a consumed by 100 g of sample (mg Br/100g).
specific time delay. It is an estimation of the alkene (olefinic) content
Chemistry in the sample i.e. of the unsaturation of carbon-
carbon chemical bonds.
Coulometric generation reagent:
- -
2 Br → Br2 + 2 e Each carbon-carbon chemical double bond (C=C)
Br2 addition to C=C double bonds: reacts with two bromine atoms:
-
Br2 + H2C=CH2 → H2BrC CBrH2
ICEQ ∗ 159.808 ∗ 100
Solutions Br − Index =
96′ 485.3399 ∗ 2 ∗ m
Titrant: Electrochemically generated bromine, Br2
ICEQ ∗ 0.0828147
Chemicals: 125 mL mercury-free electrolyte Br − Index =
m
solution according to ASTM D1492-13 (See
ICEQ: electrical current needed up to endpoint
"Sample preparation and procedure" for the
(mC)
composition of the electrolyte)
m: sample size (g)
Sample: Standard solution of cyclohexene in M(Br2): molecular mass of Br2 = 159.808 g/mol
toluene 0.055 vol% C6H10 / C7H8 (~ 100 mg 96'485.336 = Faraday-constant (C/mol)
Br/100g) 2 = equivalent number (2 Br atoms for 1 C=C)
100 = conversion factor to mg/100g
 Titration Excellence T5 (30252672), Titration If the electrolyte solution in the titration cell
Excellence T7 (30252675) or T9 becomes turbid it has to be replaced.
(30252676). Use back-weighing from a syringe for the sample
 XPE205 Analytical balance (30087653) addition. See the following table for recommended
 Coulometric KF kit without diaphragm sample sizes and recommended generation
(30267113) consists of: currents according to ASTM D1492-13:
 Coulometer board
 Complete Solvent Manager set
Estimated Specime Generation Mettler-
 Complete KF titration arm
Bromine n weight Current Toledo
 Complete titration vessel
Index [g] [mA] Method
 Generator electrode without diaphragm
0-20 1.000 1.0 M716
 DM143-SC electrode with non-PnP cable
20-200 0.600 5.0 M717
Results
200-2000 0.060 5.0 M717
Sample size R1: Bromine Index
[g] [mg/100g]
1 0.5265 104.0 The method includes a method function Pretitration
2 0.5211 103.0 to reach an initial starting potential of 35 mV. The
3 0.5174 103.0 Pretitration is performed before every sample.
4 0.5889 102.5
5 0.5808 102.7
6 0..5467 102.9
Mean 103.0
s 0.6
srel 0.504 %

A 5-pin generator cable is used with the SENSOR2 is used for IPol/UPol titration:
coulometer kit:
For bromine index determination we recommend

the generator electrode without a diaphragm, as it
is easier to clean.
This application does not replace the ASTM
Standard.
T C
Dispose as organic solvents.
References
T: 5-pin cable of Excellence titrators, enables
1 and 5 mA current ASTM D1492-13: Standard Test Method for
C: 1-pin cable of CxS instruments Bromine Index of Aromatic Hydrocarbons by
Coulometric Titration. www.astm.org
The coulometer board (CoulB) has to be placed in Further information

position E of the back and the ventilation grid http://www.mt.com/global/en/home/products/Labo
placed at the position below.
ratory_Analytics_Browse/Product_Family_Browse_
titrators_main/Titration_Excellence.html
Coulometer board (CoulB)

Measured values
Cyclohexene/toluene sample 1/6
Consumption Increment Signal Change Time

mC mC mV mV s
0.0 NaN 85.1 NaN 0
0.0 0.0 86.8 1.7 1
4.5 4.5 86.8 0.0 2
9.0 4.5 86.6 -0.2 3
13.5 4.5 86.1 -0.5 4
18.0 4.5 86.0 -0.1 5
22.5 4.5 85.7 -0.3 6
27.0 4.5 84.2 -1.5 7
31.5 4.5 84.2 0.0 8
36.0 4.5 83.7 -0.5 9
40.5 4.5 83.8 0.1 10
… … … … …
652.5 0.0 34.3 0.2 176
652.5 0.0 34.3 0.0 177
657.0 4.5 34.7 0.4 178
661.5 4.5 34.2 -0.5 179
661.5 0.0 34.6 -0.6 180
661.5 0.0 34.6 0.0 181
661.5 0.0 34.6 0.0 182
661.5 0.0 34.6 0.0 183
661.5 0.0 34.8 0.2 184
661.5 0.0 34.8 0.0 185

Method
009 Record
Summary Yes
Results No
001 Title Raw results No
Type Bromine Index Resource data No
Compatible with T5/T7/T9 Method No
ID M717 Series data No
Title Bromine Index ASTM Condition No
D1492 (5mA)
002 Sample
Number of IDs 1
ID 1 Cyclohexene/toluene
Entry type Weight
Lower limit 0.3 g
Upper limit 0.7 g
Density 0.865 g/mL
Number of sample factors 0
Temperature 25.0°C
Entry Arbitrary
003 Titration stand (KF Stand)

Type KF Stand
Titration stand KF Stand
004 Pretitration
Termination delay 10 s
005 Mix Time

Duration 10 s
006 Titration (EP Coul)

Sensor
Type Polarized
Sensor DM143-SC
Unit mV
Indication Voltametric
Ipol 2 µA
Stir
Speed 45 %
Control
End Point 35.0 mV
Generation current Fix
Current 5 mA
Termination
At EP Yes
Termination delay 40 s
Max. time s
007 Calculation R1
Result Bromine Index
Result unit mg/100g
Formula R1 = ICEQ*C/m
Constant C= 0.0828147
Decimal places 1
Result limits No
Send to buffer No
008 End of Sample


M728 – Bromine Number, ASTM D1159
Automated Bromine Number Determination of

Petrol According to ASTM D1159-01
A blank value is determined and stored as

Introduction
blank value B[ASTM D1159]. It is determined
Bromine number is the analytical procedure for every new batch of solvent mixture.
designed to determine the degree of unsaturation 2. Titrant preparation: Dissolve 10.2 g KBr and
or hydrocarbons or content of reactive C=C double 2.78 g of KBrO3 with deion. water into a 1 L
bonds. These double bonds are contained in volumetric flask and fill up to the mark. The
different hydrocarbons present in petroleum salts are first dried at 105°C (220 F) during
products. 30 minutes. The titrant can also be bought
This application note describes the fully commercially. The commercially available
automated determination of bromine number in product can be used without further
petroleum products by titration with a bromide- standardization.
bromate solution using the InMotion water bath 3. Fill the conditioning beaker with Glacial acetic
rack and a thermostat. The titration is monitored acid and the special beaker 1 with ASTM
by a platinum double pin electrode DM143 at a D1159 solvent
fixed polarization current (voltametric indication). 4. Start the method: 60 mL of solvent are added
to the titration beaker and cooled to 5 °C.
Sample preparation and procedures 5. The sample is added with a dosing unit and
1. Bromine Number solvent preparation: the titration takes place
714 mL glacial acetic acid, 134 mL 1,1,1-
trichloroethane, 134 mL methanol and 18 mL
H2SO4 (16% v/v) are mixed in 1 L vol.
flask.
Lauda Thermostat

Chemistry Remarks
- - +
BrO3 + 5 Br + 6 H → 3 Br2 + 3 H2O The Br2-number is an indication of the quantity of
bromine reactive constituents. It represents the
amount (g) of Br2 which reacts with 100 g
R1-CH=CH-R2+Br2 → R1-CHBr-CHBr-R2
sample under the conditions of the standard test
Solutions method.
Titrant: Bromide-bromate solution, The method parameters have been optimized for
Br-/BrO3-c(Br2) = 0.05 mol/L the above mentioned sample. It may be necessary
to slightly adapt the method to your specific
Chemicals: 50 mL ASTM D1159-01 solvent sample.
(see Preparation and procedures) This application does not replace the ASTM
1. Sample: Petrol standard.
Instruments and accessories By maintaining a temperature between 0°C and

5°C only the bromine addition reaction takes
 Titration Excellence T7(30252675) / T9
place. Substitution and oxidation are strongly
(30252676)
reduced, i.e. mostly avoided.
 InMotion Pro Base (30094122)
 Water Bath Rack InMotion Pro (30094139) Sample size for bromine number < 50: Direct
 Lauda Eco Silver Thermostat titration:
 2 additional dosing units (51109030)
Depending on the Br2-number, the appropriate
 XPE205 Balance (30087653)
amount of sample has to be directly injected into
 LabX Titration SW
 PP Titration beakers, 100 mL (51109388) the titration beaker:
 Burette DV1010 10 mL (51107501)
 Optional : Estimated Bromine Sample size
 Heat exchanger for thermostating (23834) number [g]
 DM40(51337000) / DM50(51337002) 1–5 6.0 – 1.2
Results 5 – 10 1.0 – 0.6
Sample R1: Temperature R2:Bromine Number 10 – 20 0.5 – 0.3
[C] [g/100g] 20 – 50 0.25 – 0.1
1 5 21.04698
2 5 20.18857
Sample size for bromine number > 50: Dilution
3 5 20.33925
4 5 20.07898 10 mL of 1,1,1-trichloroethane are placed in a 50
5 5 20.40203 mL flask and a test specimen is added as
6 5 20.34039 indicated below:
7 5 20.85292
8 5 20.93853 Estimated Bromine Sample size
9 5 20.59152 number [g]
10 5 20.72622 50 – 100 1.0 – 1.6
Mean 20.49539
100 – 200 0.5 – 0.4
s 0.29820
srel 1.455% 200 – 500 0.35 – 0.15
The sample mass (m’) is obtained by back-

weighing

Fill the flask to the mark with 1,1,1-trichloroethane
and mix
A 5 mL aliquot of this solution is injected into the

beaker together with 60 mL of solvent
Take care to enter m’/10 as sample mass
The sample was added by a dosing unit for full

automation. In order to know the sample weight
the density was determined beforehand with a
DM40 density meter: d(Petrol) = 0.7002 g/mL. Lauda Eco Silver thermostat
Do not cool below 0.0 °C, because this would
Cooling procedure: Firstly 60 mL solvent was
lead to water condensation on the water bath
dispensed with a dosing unit. Then, this solvent
rack. This water condensate can enter the
was cooled to 5 °C. Secondly the petrol was
electronics of the InMotion autosampler.
added with a second dosing unit. An additional
temperature measurement makes sure that the This setup has been tested at 20 °C and for a
temperature drops again below 5 °C. Then the relative humidity of ~ 50 %. If these conditions
sample was titrated. This procedure ensures that cannot be guaranteed (for example: higher
no sample evaporates prior to titration. humidity and higher temperatures), we
recommend using a glass cool finger that can
also be connected to a thermostat. For faster
cooling also two glass fingers can be used at the
same time.
Manual titration stand with one glass cool finger

InMotionPro with water bath rack and Cover Up lid
handling Dispose the waste as halogenated organic solvent
Additional lid-handling also reduces sample References
evaporation as well as decreases the amount of
solvent and sample vapor entering the ASTM D1159-01, “Standard Test Method for
environment. Bromine Numbers of Petroleum Distillates and
Commercial Aliphatic Olefins by Electrometric
The temperature was set to 0.5 °C on the Titration”, www.astm.org
thermostat, so that a final temperature in the
titration beaker of most 5 °C could be achieved. Further information
http://www.mt.com/global/en/home/products/Labo

Measured values
Volume dV/dt Potential Time Temperature

[mL] [mL/s] [mV] [s] [°C]
0 0 816.3 0 4.9
0 0 807.1 1 4.9
0.004 0.0035 780.7 2 4.9
0.014 0.0085 720.3 3 4.9
0.029 0.0115 692.3 4 4.9
0.046 0.013 700.5 5 4.9
0.0625 0.0125 682.4 6 4.9
0.0795 0.013 677.7 7 4.9
0.0945 0.0125 680.6 8 4.9
9.5535 0.002 150.9 765 5.3
9.559 0.0045 147.3 766 5.3
9.559 0 144.9 767 5.3
9.559 0 144.4 768 5.3
9.559 0 146.8 769 5.3
9.559 0 146.4 770 5.3
9.559 0 145.7 771 5.3
9.559 0 146.9 772 5.3
9.559 0 146.8 773 5.3
9.559 0 147.9 774 5.3
9.559 0 148.2 775 5.3
9.559 0 147.1 776 5.3
9.559 0 147.2 777 5.3
9.559 0 148.8 778 5.3
9.559 0 148.2 779 5.3

Unit °C
Method Stir
Speed 30 %
Acquisition of the measured values
Acquisition Set Value
001 Title Mode T within range
Lower limit 0 °C
Type General titration Upper Limit 5 °C
Compatible with T7/T9/T70/T90 t (max) 4000 s
ID M728 Mean value No
Title Automated Bromine Condition
Number Determination of Condition No
Petrol according to ASTM
D1159-01 009 Dispense (normal) [2]
…
Titrant Petrol
002 Sample Concentration 1
Volume 0.5 mL
Number of IDs 1 Dosing rate 1 mL/min
ID 1 Petrol Condition No
Entry type Weight
Lower limit 0.0 g
Upper limit 5.0 g 010 Stir
Density 1.0 g/mL Speed 30 %
Correction factor 1.0 Duration 10 s
Temperature 25.0°C Condition No
Entry Arbitrary
Sample data reader None
011 Measure (normal) [2]
003 Titration stand (InMotion T/Tower A) Sensor
Type InMotion T/Tower A Type Temperature
Titration stand InMotion T/1A Sensor DT1000
Lid Handling Yes Unit °C
Temperature measurement Yes
004 Auxiliary instrument
Temperature sensor DT1000
Control type RS-232 Unit °C
Name Thermostat Stir
Send output sequence Yes Speed 30 %
Output sequence OUT_SP_00_0.50\013 Acquisition of the measured values
\010 Acquisition Set Value
Wait for input sequence No Mode T within range
Condition No Lower limit 0 °C
Upper Limit 5 °C
005 Auxiliary instrument t (max) 4000 s
Mean value No
Control type RS-232
Condition
Name Thermostat
Condition No
Send output sequence Yes
Output sequence START\013\010
Wait for input sequence No 012 Calculation R1
Condition No
Result Temperature
Result unit °C
006 Dispense (normal) [1] Formula R1=T
Constant C=1
Titrant ASTM D1159 Solvent
M M[None]
Concentration 1
z z[None]
Volume 60 mL
Decimal places 1
Dosing rate 60.0 mL/min
Result limits No
Condition No
007 Stir Send to buffer No
Write to RFID None
Speed 30 %
Condition No
Duration 15 s
Condition No
013 Titration (EP) [1]
008 Measure (normal) [1] Titrant
Titrant Bromine
Sensor
Type Temperature
Sensor
Sensor DT1000
Type Polarized
Unit °C
Sensor DM143-SC
Unit mV
Temperature measurement Yes
Temperature sensor DT1000
Ipol 10 µA
Temperature acquisition Record statistics Yes
Temperature measurement Yes Extra statistical func. No
Temperature sensor DT1000 Send to buffer None
Unit °C Write to RFID None
Stir Condition No
Speed 30 %
Predispense 015 Conditioning
Mode None
Interval 1
Wait time 0s
Control
Time 20 s
Control Normal
Speed 30 %
Tendency Negative
Lid Handling No
End Point value 150 mV
Condition No
Control band 0.1 mV
Dosing rate (max) 1 mL/min
Dosing rate (max) 350 µL/min 016 Conditioning
Termination Interval 1
At EP Yes Position Special beaker 1
Termination delay 15 s Time 20 s
At Vmax 10 mL Speed 30 %
Max. time s Lid Handling No
Accompanying stating Condition No
Condition 017 End of sample
Condition No
014 Calculation R2 018 Auxiliary instrument

Result Bromine Number Control type RS-232
Result unit g/ 100g Name Thermostat
Formula R2 = (QEND-B{ASTM Send output sequence Yes
D1159 ]*C/m) Output sequence STOP\013\010
Constant C = M/(10*z) Wait for input sequence No
M M[Bromine] Condition No
z z[Bromine]
Decimal places 5
Result limits No

Mercaptan

Mercaptan
Mercaptan
Sulfur compounds are the major source of acidic species in used oil. It is therefore important to measure the
amount of sulfur in oil to prevent corrosion of engines. Furthermore, the burning of oil containing sulfur
compounds releases sulfur dioxide that reacts with the air humidity to form acidic compounds. By falling back
to the earth surface, the acid rains can damage buildings and the environment.
Mercaptan is the major source of sulfur in oil and can be measured according to several international standards
(see Table 4). Other sulfur compounds like hydrogen sulfide and polysulfides can also be found in oils. The
presented application method M695 accounts for the measurement of mercaptan, hydrogen sulfide and
polysulfides and offers a way to automatically assign the right equivalence points to the right species, according
to UOP163-10.
Standard Description of test Mettler-Toledo Titration method

ASTM D3227 Thiol (mercaptan) Sulfur in Light Distillates M373
IP 342 Thiol (mercaptan) Sulfur in Distillates
ISO 3012 Thiol (mercaptan) Sulfur in Distillates
UOP 163 Hydrogen Sulfide and Mercaptan Sulfur in Liquid Hydrocarbons M695
UOP 212 Hydrogen Sulfide, Mercaptan Sulfur, and Carbonyl Sulfide in
Hydrocarbon Gases
Table 4: Standards for the determination of Mercaptan

M695 – Mercaptan according to UOP 163-10
H2S and Mercaptan Sulfur Content in

Petroleum Products According to UOP 163-10

Introduction
1. Prepare the titrant by diluting 100 mL of a
The sulfur content of fuels is a key parameter in
solution of AgNO3 0.1 mol/L to 1 L with 2-
their quality control, and its limits are defined by
propanol
strict quality standards. A high content of sulfur in
2. Prepare the solvent by dissolving 1.6 g of
fuel leads to inefficient combustion and to the
anhydrous sodium acetate (NaC2H3O2) in
formation of corrosive, acidic deposits that
25 mL deion. water and pour into a 1 L flask.
damage the metal components of the engine.
Fill up to the mark with 2-propanol
Furthermore, combustion of sulfur-containing fuel
3. Dissolved oxygen is removed by purging the
produces sulfur dioxide gas, which leads to the
solvent and the titrant solutions with nitrogen
formation of acidic components when in contact
gas for at least 10 min prior to use. The
with moisture of the air. As a consequence, it is
solutions must be kept under nitrogen
responsible for acid rains that damage the
atmosphere.
environment and building structures.
4. Before sample analysis, a blank value is
This note describes the determination of hydrogen determined and is saved as B[UOP163].
sulfide (H2S), polysulfides (R-SS-H), and alkyl 5. For accurate sampling, sample was added
mercaptans (RSH) in petroleum products with a pipette instead of weighing (volatility).
according to UOP 163-10. The UOP 163 Thus, its density must be taken into account.
laboratory test method describes how the different The density was measured on a METTLER
curve types should be evaluated. TOLEDO DM45 density meter.
The samples are titrated potentiometrically with 6. A doctor test is performed to detect the
silver nitrate in 2-propanol. The titration is presence of H2S, as described in the UOP
monitored with a sulfidized silver ring electrode. 41-07.

7. By starting the method, the correction factor Results
for each sample is set to f = 1 if the doctor
R2: Content RSH
test was positive and to f = 0 if the doctor test
[ppm]
was negative.
1 42.33
8. 30 mL solvent are automatically added into
2 40.90
the beaker using the PowerShower™ of the
3 40.58
InMotion™ sample changer.
4 40.81
5 41.31
Chemistry 6 41.50
7 41.65
Hydrogen sulfide (H2S), M=32.06 g/mol, z=2
Mean 41.30
Mercaptan sulfur (RSH), M=32.06 g/mol, z=1
s 0.60
R-SH + AgNO3 = R-S-Ag + HNO3
srel 1.45%
R = H for H2S The tested sample, gasoline, shows only one
R = alkyl chain for mercaptan mercaptan peak. The average mercaptan content
is 41.30 ppm. The relative standard deviation srel
Solutions over 7 samples shows a good repeatability.
Titrant: Silver nitrate in 2-propanol, AgNO3,
c(AgNO3) = 0.1 mol/L
Remarks
Chemicals: 30 mL of solvent: The DMi141-SC electrode (or the Ag850) needs
1.6 g/L anhydrous sodium acetate in 2-propanol sulfidation prior to use:
Standard: Sodium chloride solution, NaCl,
c(NaCl)=0.02 mol/L, 2 mL Place the electrode during 10 minutes in an 2%
aqueous sodium sulfide solution. Subsequently,
place it in a 10% aqueous sodium sulfide
Instruments and accessories solution during 12 h (overnight).
 Titration Excellence T5 (30252672), Titration
Alternatively, you can run 3-5 test titrations with
Excellence T7 (30252675) or T9
sulfide aqueous solution. The metal ring will be
(30252676). (T9 is used for automatic
covered by a Ag2S layer after a few trials. Note that
calculations with "if….then" functionality)
it may be necessary to repeat the sulfidation.
 XP205 Analytical balance (11106027)
 Sulfidized DMi141-SC electrode (51109530) The combined DM405-SC electrode is already
(or DM405-SC (51109291), or sulfidized sulfidized and can be used right away.
InLab® Redox Ag850 (59904408) with an
InLab® Mono Plus reference electrode Depending on the mercaptan content, different
(51343196)) sample amounts are suggested:
 Burette DV1010 10 mL (51107501) Mercaptan content Suggested sample size
 Compact Stirrer (51109150) [ppm] [g]
 InMotion™ Pro Base (30094122)
0.5 – 1.0 100
 InMotion™ Pro Rack Kit 100 mL
1.0 – 100 50
(30094131)
100 – 300 10
 Lid Handling CoverUp™ InMotion™ Pro 100
300 – 500 5
mL (30094254)
 LabX® software
 Titration beakers PP 100 mL (101974) Depending on the presence of H2S and free sulfur
 20 mL Rainin pipette in the sample, the titration curve can have 1, 2 or
3 EQP’s. This method allows for the proper and
automatic assignment of all possible EQPs.

The first step is the detection of H 2S using the 4. Curve with 2 EQP’s, negative doctor test:
“Doctor test” according to UOP 41-07. Put a wet There is elemental sulfur present in the sample
piece of lead acetate paper in the vapors of the that forms polysulfides RSSH. Thus, the first EQP
samples for about one minute. If the paper turns is ignored, and the total titrant consumption up to
silver-black, hydrogen sulfide is present. This is a the second EQP is considered as caused by
positive test. If the color remains unchanged or the mercaptan R-SH.
paper darkens with a tan to yellow coloration, the
5. Curve with 3 EQPs, positive doctor test:
test is considered as negative.
The first EQP is caused by the titration of the H2S.
Five scenarios have to be considered (see
The second EQP is caused by elemental sulfur
Figure 1):
and is ignored.
1. Curve with 1 EQP, positive doctor test:
The third EQP is caused by mercaptan. The total
The EQP is caused by titration of H2S
titrant consumption between the first and the third
2. Curve with 1 EQP, negative doctor test: EQP is taken since it is caused to mercaptans.
The EQP is caused by titration of mercaptan RSH
To assign the proper substance to each EQP, a
3. Curve with 2 EQPs, positive doctor test: series of calculations is used in the method. For
The first EQP is caused by the titration of H2S. T9, conditions are used in every calculation
method function (see Table 1).
The second EQP is caused by the titration of RSH.
As no conditions are available for T5 and T7, all
results that are not needed are set to zero or NaN
(not a number) (see Tables 2 and 3).
Figure 1: Potentiometric Titration Curves of Sulfur Species in Gasoline
Result Formula Condition Valid for n EQPs

ppm H2S R1 = Q1*C/m f=1 1, 2 or 3
ppm RSH R2 = Q1*C/m nEQ = 1 AND f = 0 1
ppm RSH R3 = Q2*C/m nEQ = 2 AND f = 1 2
ppm RSH R4 = (Q1+Q2)*C/m nEQ = 2 AND f = 0 2
ppm RSH R5 = (Q2+Q3)*C/m nEQ = 3 AND f = 1 3
Table 1: Calculations and conditions for the T9 method

Result Formula nEQ/test R1 R2 R3 R4 R5
ppm H2S R1 = Q1*C*f/m 1+ xxx 0 NaN NaN NaN
ppm RSH R2 = Q1*C*(1-f)*(2-nEQ)/m 1- 0 xxx NaN NaN NaN
ppm RSH R3 = Q2*C*f*(3-nEQ)/m 2+ xxx 0 xxx 0 NaN
ppm RSH R4 = (Q1+Q2)*C*(1-f)/m 2- 0 0 0 xxx NaN
ppm RSH R5 = (Q2+Q3)*C*f/m 3+ xxx 0 0 0 xxx
Table 2: Calculations for the T5/T7 method Table 3: Identification of the correct RSH value
(xxx = result, NaN = not a number)
The application method has been developed for References

the mentioned sample. It may be necessary to
UOP Method 163-10, “Hydrogen Sulfide and
optimize the method for your sample.
Mercaptan Sulfur in Liquid Hydrocarbons by
This application does not replace the UOP163-10 Potentiometric Titration”.
Standard
UOP Method 41-07, “Doctor Test for Petroleum
Waste disposal and safety measures Distillates”.
After filtration, the precipitate has to be classified Analytical Chemistry UserCom 14 (10/2009
as special waste. Mettler-Toledo AG, MarCom Analytical, ME-
51725212)
The liquid phase has to be disposed as non-
halogenated organic waste. Further information
http://www.mt.com/global/en/home/products/Labo
Measured values

Volume dV/dt Potential 1st deriv. Time

[mL] [mL/s] [mV] [mV/mL] [s]
0 -326.9 0
0.05 0.05 -410.2 30
0.1 0.05 -417.7 36
0.225 0.125 -423.2 42
0.5375 0.3125 -421.3 47
0.9375 0.4 -415.6 59.44 52
1.3375 0.4 -400.3 49.16 61
1.447 0.1095 -395.4 53.68 67
1.6015 0.1545 -388.2 65.43 74
1.7675 0.166 -377.2 85.69 82
1.851 0.0835 -371.5 107.53 88
1.966 0.115 -358.5 173.23 97
2.016 0.05 -352 256.28 103
2.069 0.053 -342.7 351.78 110
2.119 0.05 -333.6 525.79 117
2.169 0.05 -309.1 840.91 132
2.219 0.05 -263.7 1152.25 155
2.259098 -190.2 1182.01 EQP
2.269 0.05 -172 1181.08 185
2.319 0.05 -92.4 902.01 215
2.369 0.05 -70.7 626.38 226
2.4365 0.0675 -52.9 351.03 233
2.4865 0.05 -39.3 269.58 242
2.5365 0.05 -32.4 207.66 248
2.6495 0.113 -21.4 116.56 254
2.766 0.1165 -9.7 87.25 260
2.843 0.077 -3.9 75.21 266
2.9875 0.1445 4.5 59.48 272
3.165 0.1775 13.2 48.39 278
3.3565 0.1915 20.4 38.88 284
3.637 0.2805 29.5 29.91 289
3.9205 0.2835 37.5 24.4 294
4.249 0.3285 44.4 20.19 299
4.649 0.4 50 16.63 304
5.049 0.4 57.4 14.4 309
5.449 0.4 62.9 13.02 314

Ranges 0
Method for T9 Add. EQP criteria Steepest jump
Steepest jumps 3
001 Title
Termination
Type General titration At Vmax 10 mL
Compatible with T9 At potential No
ID M695_T9 At slope No
Title Mercaptan content in oil After number of recognized EQPs Yes
… Number of EQPs 3
002 Sample Accompanying stating
Number of IDs 1 Accompanying stating No
ID 1 -- Condition
Entry type Volume Condition No
Lower limit 0.0 mL
Upper limit 30 mL 007 Calculation R1
Density 0.761 g/mL Result Content H2S
Correction factor 0.0 Result unit ppm
Temperature 25.0°C Formula R1 = (Q-B[UOP163])
Entry Arbitrary *C/(m*d)
InMotion reader None Constant C = M*1000/z
M M[Hydrogen sulfide]
003 Titration stand (InMotion T/Tower A) z z[Hydrogen sulfide]
Decimal places 3
Type InMotion T/Tower A
Result limits No
Titration head position Sample
Lid handling No
Send to buffer No
004 Pump Condition Yes
Auxiliary reagent Solvent Formula nEQ=1 AND f=0
Volume 30 mL
Pump property 1-way 008 Calculation R2
Condition No
Result Content RSH
Result unit ppm
005 Stir Formula R2 = (Q-B[UOP163])
Speed 35 % *C/(m*d)
Duration 15 s Constant C = M*1000/z
Condition No M M[Mercaptan sulfur]
z z[Mercaptan sulfur]
006 Titration (EQP) [1] Decimal places 3
Result limits No
Titrant
Titrant AgNO3 in 2-Propanol
Send to buffer No
Sensor
Type mV
Condition Yes
Sensor DM141-SC
Formula nEQ=1 AND f=0
Unit mV
Temperature measurement No 009 Calculation R3
Stir Result Content RSH
Speed 35 % Result unit ppm
Predispense Formula R3 = Q2*C/(m*d)
Mode None Constant C = M*1000/z
Wait time 0s M M[Mercaptan sulfur]
Control z z[Mercaptan sulfur]
Control User Decimal places 3
Titrant addition Dynamic Result limits No
dE (set value) 8.0 mV Record statistics Yes
dV (min) 0.05 mL Extra statistical func. No
dV (max) 0.4 mL Send to buffer No
Mode Equilibrium controlled Write to Smart Tag None
dE 1 mV Condition Yes
dt 2s Formula nEQ=1 AND f=1
t (min) 5s
t (max) 30 s 010 Calculation R4
Result Content RSH
Procedure Standard
Result unit ppm
Threshold 150 mV/mL
Formula R4 = (Q+Q2-B[UOP163]
Tendency None

)*C/(m*d)
Constant C = M*1000/z Method for T5/T7
M M[Mercaptan sulfur]
z z[Mercaptan sulfur] 001 Title
Decimal places 3 Type General titration
Result limits No Compatible with T5/T7/T9
Record statistics Yes ID M695_T5_T7
Extra statistical func. No Title Mercaptan content in oil
Send to buffer No for T7 and T5
Write to Smart Tag None …
Condition Yes
002 Sample
Number of IDs 1
011 Calculation R5
ID 1 --
Result Content RSH Entry type Volume
Result unit ppm Lower limit 0.0 mL
Formula R5 = (Q2+Q3)*C/(m*d) Upper limit 30 mL
Constant C = M*1000/z Density 0.761 g/mL
M M[Mercaptan sulfur] Correction factor 0.0
z z[Mercaptan sulfur] Temperature 25.0°C
Decimal places 3 Entry Arbitrary
Result limits No InMotion reader None
003 Titration stand (InMotion T/Tower A)
Send to buffer No
Write to Smart Tag None Type InMotion T/Tower A
Condition Yes Titration stand InMotion T/1A
Formula nEQ=3 AND f=1 Titration head position Sample
Lid handling No
012 Rinse
004 Pump
Rinse cycles 1 Auxiliary reagent Solvent
Vol. per cycles 20 mL Volume 30 mL
Position Current position Pump property 1-way
Drain No Condition No
Condition No
005 Stir
013 End of sample Speed 35 %
Duration 15 s
Condition No
014 Park
006 Titration (EQP) [1]
Condition No Titrant
Titrant AgNO3 in 2-Propanol
Sensor
Type mV
Sensor DM141-SC
Unit mV
Temperature measurement No
Stir
Speed 35 %
Predispense
Mode None
Wait time 0s
Control
Control User
Titrant addition Dynamic
dE (set value) 8.0 mV
dV (min) 0.05 mL
dV (max) 0.4 mL
Mode Equilibrium controlled
dE 1 mV
dt 2s
t (min) 5s
t (max) 30 s
Procedure Standard

Threshold 150 mV/mL 010 Calculation R4
Tendency None
Result Content RSH
Ranges 0
Result unit ppm
Formula R4 = (Q+Q2-B[UOP163]
Steepest jumps 3
)*C*(1-f)/(m*d)
Termination
Constant C = M*1000/z
At Vmax 10 mL
At potential No
At slope No
Decimal places 3
Result limits No
Number of EQPs 3
Accompanying stating
Send to buffer No
Condition
Condition Yes
Condition No
007 Calculation R1
011 Calculation R5
Result Content H2S
Result unit ppm Result Content RSH
Formula R1 = (Q-B[UOP163]) Result unit ppm
*C*f/(m*d) Formula R5 = (Q2+Q3)*C*f/
Constant C = M*1000/z (m*d)
M M[Hydrogen sulfide] Constant C = M*1000/z
z z[Hydrogen sulfide] M M[Mercaptan sulfur]
Decimal places 3 z z[Mercaptan sulfur]
Result limits No Decimal places 3
Record statistics Yes Result limits No
Extra statistical func. No Record statistics Yes
Send to buffer No Extra statistical func. No
Write to Smart Tag None Send to buffer No
Condition Yes Write to Smart Tag None
Formula nEQ=1 AND f=0 Condition Yes
008 Calculation R2
012 Rinse
Result Content RSH
Result unit ppm Auxiliary reagent Solvent
Formula R2 = (Q-B[UOP163]) Rinse cycles 1
*C* (1-f)*(2- Vol. per cycles 20 mL
nEQ)/(m*d) Position Current position
Constant C = M*1000/z Drain No
M M[Mercaptan sulfur] Condition No
Decimal places 3 013 End of sample
Result limits No
014 Park
Send to buffer No Titration stand InMotion T/1A
Write to Smart Tag None Position Conditioning beaker
Condition Yes Condition No
009 Calculation R3
Result Content RSH
Result unit ppm
Formula R3 = (Q2*C*f*(3-nEQ))
/(m*d)
Decimal places 3
Result limits No
Send to buffer No
Condition Yes

Water content

Water content
Water content
Even though water and oil don’t mix, a small amount of water is always present. Water can influence physical
and chemical proprieties of oil. It can for example modify the viscosity of lubricants or react with basic
additives, leading to the formation of acid components, sludge or varnish. It is therefore primordial to be able to
measure the water content of oil to prevent costly machine damages.
Several possibilities exist to measure the water amount in oil components including the crackle test, calcium
hydride test, infrared spectroscopy or Karl Fischer titration. Karl Fischer titration is the most precise and widely
used technique for this application. Both volumetric and coulometric Karl Fischer titration can be used,
depending on the type of oil and on the amount of water that it contains. Numerous standards exist on the water
determination in oil, see Table 5.
Direct sample addition to the titration cell can be used but it requires the proper solvent mixture and frequent
solvent exchange to avoid solubility issues. Another solution is the use of the InMotion KF, an automated
external oven that extracts water from the sample and transfers it to the titration cell.
In the present brochure, two examples of water determination using the InMotion KF are described:
- Water content in lubricant, application note M734
- Azeotrope water extraction in brake fluid, application note M731

DIN 51777 Water in Solvents/Hydrocarbons (Volumetric and Coulometric)
Coulometric Determination
ASTM D4928 Water in Crude Oils
ASTM D6304 Water in Petroleum Products M680
ASTM E1064 Water in Organic Liquids M354
IP 386 Water in Crude Oils
ISO 10337 Water in Crude Oils
ISO 12937 Water in Petroleum Products M328, M490
UOP 481 Water in Liquid Hydrocarbons M450
Volumetric Determination
ASTM D1364 Water in Volatile Solvents M302
ASTM E203 Water in General Samples M356
IP 471 Water in Distillates
ISO 6296 Water in Petroleum products M481, M307
Table 5: Standards for the determination of water in oil.

M734 – Water content of a Lubricant with InMotion KF
Water Content of a Lubricant with InMotion KF

Introduction
Lubricants are commonly used to reduce friction 9. Scan principle: A sample with an unknown
between surfaces that are in mutual contact. water gas-phase extraction temperature is
Therefore lubricants will reduce heat that is heated with a constant heating rate from a
generated when these surfaces move a long each defined start to a defined end temperature.
other. Prominent lubricants are cutting and The released water is monitored as function of
grinding oils that are being used in various temperature. The qualitative interpretation of
industrial processes such as abrasive machining the curve allows to define the optimal gas-
or drilling with high speed tools. phase extraction temperature.
10. Long Needle: Use the long needle that is
In this application the water content of a lubricant available for the 5 mL vial size for the sample
with medium water content was titrated using a analysis. This long needle will allow purging
C30S connected to an InMotion KF sample through the lubricant and, thus, liberating all
changer. A longer needle allows to purge through water from it.
the oil making sure that all water is completely 11. Blank preparation: Place three empty 5 mL
removed and transferred into the titration cell. blank vials into positions 1 ─ 3 of the
InMotion KF. Both vials are closed with the
screw cap.
Dry Air
To Vessel
Inner Needle
Outer Needle

12. Oil preparation: Add ~ 2.0 g lubricant with a Results
syringe into a 5 mL vial and close it with the
R2: Water content
screw cap. Place all filled vials into the
Blank: [µg], Sample: [ppm]
corresponding positions of the InMotion KF
Blank 1 37.2
rack.
Blank 2 45.7
13. Start of analysis: Place an empty vial that is
Blank 3 42.4
closed with a screw cap into the drift position
1 1160.5
on the rack. Start M734. The method will
2 1219.9
perform firstly a pretitration to remove excess
3 1214.2
water from the titration cell and will
4 1221.0
subsequently go into the Standby modus.
5 1208.9
Perform manual drift determinations until the
6 1214.8
online drift value is < 5 µg/min. Then press
7 1211.1
"Start sample". The method will usually start
8 1212.2
with the following sequence: Drift – Blank –
9 1211.8
Sample. In most cases the drift is determined
10 1202.4
once before the sample loop and this drift
11 1219.8
value is used for all subsequent calculations.
12 1214.3
Chemistry 13 1221.7
14 1217.0
Water, M = 18 g/mol.
15 1197.7
16 1218.3
ROH + SO2 + 3 RN + I2 + H2O = (RNH)•SO4 R + 17 1217.0
2 (RNH)I 18 1215.8
19 1215.6
20 1195.2
Solutions 21 1218.4
Reagent: Coulomat AG oven 22 1220.4
23 1194.9
Standard: 1.00 % oven water standard with an
24 1207.8
actual concentration of 0.99 % water (0.99 %
Mean 1210.4 ppm
+/- 0.2 %, Expanded measurement uncertainty).
s 13.3
srel 1.095 %
 Compact line titrator C30S (30252662) Scan: The scan shows that most water is liberated
 Titration Excellence T7 (30252675) or T9 between 120 and 180 °C. Starting from about
(30252676) with coulometric Karl-Fischer kit 220 °C decomposition of the lubricant becomes
(30267113) visible as can be seen from an increased slope &
 Long needle for 5 mL vial (30407447) increasing drift starting at this temperature.
 XPE205 Analytical balance (30087653) Therefore, as gas phase extraction temperature,
 InMotion KF-Pro (30407503) 180 °C was selected, which is about 40 °C lower
 Air pump AP200 (30407441) than the observed onset temperature of
 LabX software decomposition.
 Sample vials 5 mL, with screw caps
(30407449, 30407436)
 Spatula / Syringe

Remarks Waste disposal and safety measures
Depending on the water content of the sample,
Dispose as organic solvent.
different sample sizes are recommended for
coulometric KF-titration:
References
Water content Sample size Good titration practice in Karl-Fischer Titration
[ppm] [%] [g] (30245921)
100 – 1000 ppm 20 – 2
1000 – 10'000 ppm 2 – 0.2
Measured values
6000 100
5000
75
Cumulated water (µg)
Drift (µg/min)
4000
3000 50
2000
25
1000
0 0
50 75 100 125 150 175 200 225 250
Temperature (°C)
Scan Lubricant.
3000 1600
1400
Cumulative Water [µg]
2500
1200
Drift [µg/min]
2000 1000
1500 800
1000 600
400
500 200
0 0
0 100 200 300 400 500 600
Time [s]
Sample 5/10

Consumption Meas. value H2O Drift Time
mC mV µg µg/min s
0 532 0 0 0
25.3 532.4 2.4 0 1
110.4 530.6 10.3 80.3 1
214.7 531.9 20 224.1 2
407.1 533.8 38 378.1 2
653.3 535.7 61 601.3 3
953.2 533.4 89 832.9 4
26992 105.9 2519.8 41.4 590

27004 107.5 2520.9 33.7 591
27019 108.7 2522.3 76.8 592
27038.5 104.4 2524.1 93.7 593
27043.1 99.3 2524.6 93.2 594
27043.1 99.6 2524.6 15.1 595
27043.5 100.6 2524.6 0 596
27043.5 103.4 2524.6 0 597
27051.1 104.3 2525.3 17 598
27057.2 105.5 2525.9 33.1 599
27069.2 107.5 2527 25.4 600
27076.7 103.2 2527.7 58.1 600
Sample 5/24.
Analysis start Manual

Method (Sample)
004 Titration stand (InMotion KF)

001 Title Type InMotion KF
Titration stand InMotion KF/1
Type InMotion KF Coul.
Temperature ramp No
Compatible with C30S / T7 / T9
Oven temperature 180 °C
ID M734
Source for drift Determination
Title Water in Lubricant
Max. start drift 10 µg/min
Author Administrator
Carrier gas source InMotion KF
Date/Time 04/26/2017 09:14:02 am
Flow rate 80 mL/min
Transfer tube heating No
Modified on 04/26/2017 09:15:24 am
Modified by Administrator
Protect No
005 Mix time
SOP None Duration 60 s
002 Drift determination 006 Titration (KF Coul) [1]

Wait time 60 s Sensor
Duration 3 min Type Polarized
Temperature sensor DM143-SC
Unit mV
003 Sample Indication Voltametric
Ipol 5.0 µA
Sample
Stir
Sample type Blank
Speed 45 %
Number of IDs 1
ID 1 Blank 10 ml vial
Control
Entry type Fixed pieces
End point 100.0 mV
Pieces 1 pcs.
Control band 250 mV
Weight per piece 1.0 g
Rate Normal
Start Cautious
Temperature 25.0 °C

Termination Unit mV
Type Delay time Indication Voltametric
Delay time 10 s Ipol 5.0 µA
Min. time 600 s Stir
Max. time 600 s Speed 45 %
007 Calculation R1 Control

End point 100.0 mV
Result InMotion blank value
Control band 250 mV
Result unit µg
Formula R1=(ICEQ/10.712-
Dosing rate (min) 80 µL/min
TIME*DRIFT)/C
Start Automatic
Constant C= 1
Decimal places 3
Termination
Result limits No
Type Delay time
Delay time 10 s
Min. time 600 s
Max. time 600 s
008 End of sample 015 Calculation R2

Result Cont. blank comp. (B in µg)
Result unit ppm
009 Blank Formula R2=(ICEQ[2]/10.712-
TIME[2]*DRIFT-B[Blank
Name Blank IMKF Coul IMKF Coul])/(C*m)
Value B= Mean[R1] Constant C=1
Unit µg Decimal places 3
Limits No Result limits No
010 Record Extra statistical functions No
Summary No
Results Yes
Raw results No 016 End of sample
Resource data No
Method No
017 Record
Series data No
Summary Yes
Results No
011 Sample Raw results No
Resource data No
Sample Method No
Sample type Sample Series data No
Number of IDs 1
ID 1 Lubricant Oil
Entry type Weight
Lower limit 0.0 g
Upper limit 5.0 g
Density 1.0 g/mL
Entry Arbitrary

Type InMotion KF
Temperature ramp No
Oven temperature 180 °C
Flow rate 80 mL/min
013 Mix time

Duration 60 s
014 Titration (KF Coul) [2]
Sensor
Type Polarized
Method (Scan) Extra statistical functions No
007 Record
001 Title
Summary Per sample
Type Scan KF Coul. Results Per sample
Compatible with C30S / T7 / T9 Raw results Per sample
ID Scan M734 Table of meas. values Yes
Title Scan Lubricant Sample data Per sample
Resource data Per sample
Author Administrator H2O - T Yes
Date/Time 04/25/2017 11:05:28 am Drift - T Yes
H2O - T & Drift - T Yes
Modified on 04/25/2017 11:05:28 am
Method Yes
Modified by Administrator Series data Yes
Protect No
SOP None 008 End of sample
009 Record
002 Sample
Summary Yes
Sample Results Yes
Sample type Sample Raw results Yes
Number of IDs 1 Resource data Yes
ID 1 Lubricant Oil Method Yes
Entry type Weight Series data Yes
Lower limit 0.0 g
Upper limit 5.0 g
Density 1.0 g/mL
Entry Arbitrary

Type InMotion KF
Flow rate 80 mL/min
004 Mix time

Duration 20 s
005 Titration (KF Coul) [1]

Sensor
Type Polarized
Unit mV
Ipol 5.0 µA
Temperature program
Start temperature 50 °C
Heating rate 2 °C/min
End temperature 250 °C
Stir
Speed 35 %
Control
End point 100.0 mV
Control band 250 mV
Generator current automatic
006 Calculation R1
Result Sample size
Result unit g
Formula R1=m
Constant C= 1
M M[None]
z z[None]
Decimal places 4
Result limits No

M731 – Water in Brake Fluid
Automated Water Content Determination of

Brake Fluid with InMotion KF

Introduction
1. Gas phase extraction principle: Air is
Brake fluid is a hydraulic fluid used in hydraulic
aspirated by an air pump and passed through
brakes of automobiles. Being an incompressible
a drying unit filled with silica gel and
fluid it is used to transfer force into pressure, and
subsequently through a drying unit filled with
to amplify braking force.
molecular sieve. A digital gas flow control will
DOT brake fluids are hygroscopic – they tend to regulate the flow rate (typical 80 – 150
absorb water from the environment, and this mL/min) that is defined in the titration
absorption cannot be prevented. On average, the method. The dry air will extract the water from
brake fluid in a vehicle absorbs up to 1.5 % of the sample and transfer it into the titration
water each year. As the water content of the brake cell. A long needle allows purging through the
fluid increases, its boiling point decreases. When liquid sample and, thus, liberating all water
this happens, a failure known as “vapor lock” from it.
occurs and the force applied to the pedal is not 2. Blank preparation: Apart from the water in the
transmitted to the brake cylinders, potentially sample, the sample vial also contains
leading to a failure of the brake system. This is atmospheric humidity; This makes blank
illustrated in figure 1. value determination necessary. Furthermore,
Therefore, the boiling point and the water content measurements were performed with the help
of brake fluids are essential parameters when of toluene. Therefore, the amount of toluene
considering the safety of a vehicle. (0.5 mL) that was added to the sample vials
needs to be added to the blank vials as well.
In this application the water content of a DOT Place three blank 10 mL vials with 0.5 mL
brake fluid was measured fully automatically toluene each into positions 1, 2 and 3 of the
using a volumetric V30S Karl Fischer titrator InMotion KF. All vials are closed with the
connected to an InMotion KF oven autosampler. screw cap.
This application can also be performed with a T7
or T9.
Figure 1: Brake cylinder under different moisture conditions.

Blue: brake fluid, white: moisture and vapor lock.
a) New brake fluid: newly-replaced brake fluid is devoid

of moisture
b) Acceptable levels of moisture: over time, moisture is
absorbed by the brake fluid, decreasing the boiling
point
c) Excessive moisture: after a while, the brake fluid
absorbs too much moisture and needs to be replaced
d) Vaporized moisture: if the moisture vaporizes, it can
form a vapor lock that dangerously reduces the brake
cylinder's hydraulic function

3. Sample preparation: Add ~ 0.5 g of brake Results
fluid into a 10 mL vial. Add 0.5 mL of toluene
R2: Water content
and close it with the screw cap. Place all
Blank: [µg], Sample: [%]
filled vials into the corresponding positions of
Blank 1 93.2
the InMotion KF rack.
Blank 2 81.7
4. Start of analysis: Place an empty vial that is
Blank 3 80.2
closed with a screw cap into the drift position
1 2.12
on the rack. Start M731. The method will first
2 2.26
perform a pretitration to remove excess water
3 2.20
from the titration cell and will subsequently go
4 2.18
into the Standby modus. Perform manual drift
5 2.18
determinations until the online drift value is
6 2.18
< 5 µg/min. Then press "Start sample". The
7 2.24
method will usually start with the following
8 2.19
sequence: Drift – Blank – Sample. In most
9 2.20
cases the drift is determined once before the
10 2.20
sample loop and this drift value is used for all
11 2.19
subsequent calculations. Blank value
Mean 2.19%
determination and sample determination need
s 0.04%
to be carried out using the same method
srel 1.62%
parameters.
Scan: Prior to this measurement a temperature

Chemistry
scan of the brake fluid sample (with toluene) was
Water, M = 18 g/mol. performed in order to evaluate the optimal gas
ROH + SO2 + 3 RN + I2 + H2O = (RNH)•SO4 R + phase extraction temperature. Decomposition was
2 (RNH)I observed to start at approx. 200 °C. As the
optimal oven temperature should be chosen
Solutions
20 °C – 30 °C below the decomposition
Titrant: One component reagent 5 mg H2O/mL temperature, samples were measured at 170 °C.
Chemicals: Methanol dry as solvent Sample: The value of the first sample is by trend
lower than the values of the following samples. If
Standard: 5.55 % oven water standard
sample 1 would be excluded, a mean of 2.20%
Sample: DOT brake fluid and an srel of 1.23% would be obtained.
Instruments and accessories Remarks
 Compact line titrator V30S (30252667) For the brake fluid sample, water release without
 Titration Excellence T7 (30252675) or T9
toluene was observed to be retarded and slow
(30252676)
(figure 2). With > 200 µg/min drift was high till
 XPE205 Analytical balance (30087653)
the end of the measurement time of 900s.
 InMotion KF Pro Oven Autosampler with
Elongation of the measurement time to 1500s did
10 mL rack (30407502)
not show much improvement.
 Air pump AP200 (30407441)
 Long needle for oil analysis (10 mL vial) With the help of toluene, water release was faster
(30407448) and the drift was in an acceptable range at the
 Sample vials 10 mL and screw caps for end of the measuring time of 900s (figure 3).
10 mL vials (30407445, 30407436)
 LabX software The water in the sample and the toluene form an
 Spatula / Syringe azeotropic mixture. By this the water is separated

from the sample matrix and it is pulled out of the
sample. As azeotropic mixtures cannot be
separated into their individual components by 6000
distillation, the water-toluene mixture is transferred 5000
with the carrier gas into the titration cell where the
Drift (µg/min)
4000
water content is determined by Karl Fischer 3000
titration. Furthermore, toluene reduces the 2000
accumulation of sample droplets in the transfer 1000
tube and the contamination of the cell, which 0
increases the accuracy of the measurement. 0 300 600 900

Time (s)
2500 Figure 3: Water content measurement of a brake

2000
fluid sample with addition of toluene
Drift (µg/min)
1500 Waste disposal and safety measures

1000
Dispose as organic solvent
500
References
0
0 300 600 Good titration practice in Karl-Fischer Titration
900 Time (s)
(30245921)
Figure 2: Water content measurement of a brake
fluid sample without addition of toluene
Measured values
3500 200
180
3000
160
2500 140
Drift [µg/min]
2000 120
100
1500 80
1000 60
40
500
20
0 0
50 100 150 200 250
Temperature [°C]
Scan brake fluid

12 6000
10 5000
8 4000
Drift [µg/min]
6 3000
4 2000
2 1000
0 0
0 200 400 600 800 1000
Time [s]
Water content determination sample 6/10
Volume Meas. value H2O Drift Time

mL mV µg µg/min s
0 270.3 0.0000 0.0 0
0 267.2 0.0000 0.0 0
0.00125 280.8 0.0062 0.0 1
0.00225 315.9 0.0112 191.2 2
0.00425 320.5 0.0211 226.5 3
0.00650 333.3 0.0323 318.9 4
0.00800 320.9 0.0397 388.6 5
2.23900 88.1 11.1109 0.0 887

2.23900 88.1 11.1109 0.0 888
2.23900 89.0 11.1109 0.0 889
2.23950 87.6 11.1134 0.0 890
2.23950 81.3 11.1134 14.8 891
2.23975 87.3 11.1147 14.8 892
2.24000 93.4 11.1159 22.3 893
2.24000 90.9 11.1184 29.7 894
2.24050 91.1 11.1184 44.6 595
2.24050 82.7 11.1184 44.6 896
2.24050 95.5 11.1184 223 897
2.24050 92.4 11.1184 7.4 898
2.24050 96.5 11.1184 7.4 899
2.24050 95.4 11.1184 0.0 900
Sample 6/10.

Method
Control
End point 100.0 mV
Control band 400.0 mV
001 Title Dosing rate (max) 5 mL/min
Type InMotion KF Vol. Dosing rate (min) 80 µL/min
Compatible with V30S / T7 / T9 Start Cautious
ID M731 Termination
Title Brake fluid Type Delay time
Author Administrator Delay time 10 s
Date/Time 05/11/2017 04:31:06 am At Vmax 10.0 mL
Modified on 05/11/2017 04:31:06 am Min. time 900 s
Modified by Administrator Max. time 900 s
Protect No
SOP None 007 Calculation R1
Result InMotion blank value
002 Drift determination Result unit µg
Wait time 60 s Formula R1 = (VEQ*CONC-
Duration 5 min TIME*DRIFT/1000)*C
Constant C = 1000
003 Sample Decimal places 1
Result limits No
Sample Record statistics Yes
Sample type Blank Extra statistical functions No
Number of IDs 1
ID 1 Blank with toluene
008 End of sample
Entry type Fixed pieces
Pieces 1 pcs.
Weight per piece 1.0 g 009 Record
Summary Yes
Results No
Raw results No
Concentration
Resource data No
Titrant KF 1-comp 5
Method No
Nominal conc. 5 mg/mL
Series data No
Standard Water-Standard 10.0
Entry type Weight
Lower limit 0.00 g 010 Blank
Upper limit 2.0 g Name Blank IMKF Vol
Temperature 25.0 °C Value B= Mean[R1]
Mix time 10 s Unit µg
Autostart Yes Limits No
Entry After addition
Conc. lower limit 4.5 mg/mL 011 Sample
Conc. upper limit 5.6 mg/mL
Sample
Sample type Sample
004 Titration stand (InMotion KF) Number of IDs 1
Type InMotion KF ID 1 Brake fluid with toluene
Titration stand InMotion KF/1 Entry type Weight
Temperature ramp No Lower limit 0.0 g
Oven temperature 170 °C Upper limit 5.0 g
Source for drift Determination Density 1.0 g/mL
Max. start drift 10 µg/min Correction factor 1.0
Carrier gas source InMotion KF Temperature 25.0 °C
Flow rate 80 mL/min Entry Arbitrary
005 Mix time Type InMotion KF
Duration 60 s Titration stand InMotion KF/1
Temperature ramp No
006 Titration (KF Vol) [1] Oven temperature 170 °C
Titrant KF 1-comp 5
Reagent type 1-comp
Flow rate 80 mL/min
Sensor
Type Polarized
Sensor DM143-SC
Unit mV 013 Mix time
Indication Voltametric Duration 60 s
Ipol 24.0 µA
Stir 014 Titration (KF Vol) [2]
Speed 35 %
Titrant KF 1-comp 5
Reagent type 1-comp
Sensor
Type Polarized
Sensor DM143-SC
Unit mV
Ipol 24.0 µA
Stir
Speed 35 %
Control
End point 100.0 mV
Control band 400.0 mV
Dosing rate (min) 80 µL/min
Start Normal
Termination
Type Delay time
Delay time 10 s
At Vmax 10.0 mL
Min. time 900 s
Max. time 900 s
015 Calculation R2
Result Cont. blank comp.
(B in µg)
Result unit %
Formula R2=(VEQ[2]*CONC-
B[Blank IMKF Vol]/1000-
TIME[2]*DRIFT/1000)*C/
m
Constant C = 0.1
Decimal places 2
Result limits No
016 End of sample
017 Record
Summary Yes
Results No
Raw results No
Resource data No
Method No
Series data No

Refinery Processes

Refinery Processes
Refinery Processes
During refinery processes, a large quantity of water is used, mainly for cooling purpose. Depending on its
physical-chemical proprieties, water can induce corrosion, scale formation, fouling or biological contamination
of the cooling system. To avoid a reduction of the cooling power of the system or any costly breakdown due to
these unwanted phenomena, it is important to monitor several water parameters such as total hardness,
conductivity, pH, alkalinity, acidity.
Total hardness is a measure of the calcium and magnesium carbonate concentration that has a tendency to
form scale in the cooling system.
Conductivity is a measure of the amount of dissolved material in the water.

pH, alkalinity and acidity are important factors that influence scale formation, biological contamination, and
corrosion. With low pH, and thus high acidity, corrosion processes are favored. At high pH, and thus high
alkalinity, scale formation can be promoted. When scale and corrosion problems exist, fouling will also appear
in the system.
Most of the mentioned water characteristics can be measured by titration (see Table 6).
As example of water analytics titration methods that are useful in the petroleum industry, the method M405 for
total hardness determination is presented.

ASTM D511 Water Hardness Titration M405
ASTM D1126 Water Hardness Titration
ASTM D512 Chloride in Water M359
ASTM D513 Carbon Dioxide in Water
ASTM D888 Total Dissolved Oxygen in Water
ASTM D1067 Acidity and Alkalinity in Water
ASTM D1125 Conductivity in Water M439
ASTM D1179 Fluoride in Water M442
ASTM D1252 Chemical Oxygen Demand of Water M438
ASTM D1293 pH Measurement of Water M439
ISO 10523 pH Measurement of Water
ASTM D1426 Ammonia by ISE Measurement in Water
ASTM D2036 Cyanide in Water (ISE Measurement and Titration)
DIN 38409 p- and m-Values (Acidity and Alkalinity) in Water M415, M416
UOP 209 Alkalinity, Sulfide and Mercaptide in Refinery Caustics
UOP 423 Thiosulfate in Refinery Caustics
UOP 456 Chloride in Refinery Waters
UOP 975 Fluorine in LPG by ISE
Table 6: Standards for the determination of water’s proprieties.

M405 – Total Hardness of Water
Total Hardness of Tap Water by

Photometric Titration
2. Check the transmission signal of the DP5 in

Introduction
deionized water using a manual operation
Water that contains a high concentration of and adjust it to 1000 mV by turning the knob
calcium and magnesium carbonate is considered on the top of it.
as hard water. With time and heat, scale can be 3. Perform the titer determination using 0.1
formed in pipes and water heaters. To avoid costly mol/L zinc sulfate (ZnSO4) standard solution:
breakdown, water hardness has to be monitored 5 mL ZnSO4 solution is added into a titration
for industrial processes that use tap water in beaker and diluted with 50 mL deionized
cooling towers or water heaters. Water hardness water.
can also be an issue in houses, reducing the 4. For sample measurement, pipette 50 mL tap
efficiency of soap or calcifying plumbing fixtures. water into a beaker
This note describes the determination of total 5. Start the analysis
hardness in tap water by complexometric titration 6. 1 mL 0.1 % Eriochrome Black T ethanolic
of calcium and magnesium at pH 10 using EDTA. solution is added to the sample beaker with
an additional dosing unit
The total hardness is expressed as calcium 7. The pH of the sample is adjusted to approx.
carbonate, CaCO3. During the titration, the color 10 by adding 10 mL 5 % NH3-solution with
change of the Erio T indicator (pink to blue) is an additional dosing unit
sensed by a photometric sensor DP5 8. Before starting the subsequent sample, the
Phototrode™. DP5, the tubing and the stirrer are rinsed with
Sample preparation and procedures deionized water.
1. After turning on the DP5 set to 660 nm, wait Chemistry

10-15 minutes before starting the analysis to 2+ 2+
Mg and Ca as CaCO3, M = 100.09 g/mol,
achieve a stable signal z=1
2+ 2- 2- +
Ca + EDTA-H2 → Ca-EDTA + 2H
2+ 2- 2- +
Mg + EDTA-H2 → Mg-EDTA + 2H

Solutions
Titrant: EDTA, c(EDTA) = 0.1 mol/L On the other hand, ammonia and Eriochrome
Chemicals: 5 % NH3- solution Black T can be added manually just before the
0.1 % Eriochrome Black T in ethanol titration.
Standard: 5 mL ZnSO4, c(ZnSO4) = 0.1 mol/L This analysis can also be run on a G20S with no
Instruments and accessories or one additional dosing unit.
 Titration Excellence T9 (30252676), Avoid the formation of air bubbles during titration
 T7 (30252675), T5 (30252672) or since they disturb the photometric indication.
compact titrator G20S (30252669) Thus, select the appropriate stirring speed.
 DP5 Phototrode™ (51109300)
The wavelength of the DP5 can be also set to
 2 x Dosing Unit (51109030)
555 nm instead of 660 nm. In this case, the
 3 x Burette DV1010 10 mL (51107501)
method parameter “Tendency” has to be set to
“Positive”.
 XPE205 Analytical balance (30087653)
 LabX software Add ammonia solution immediately before titration
 Titration beakers PP 100 mL (101974) and after addition of Eriochrome Black T to avoid
 Spatula/Syringe evaporation of ammonia from the sample.
Results Instead of ammonia solution, it is possible to use
borate buffer pH10. Preparation: Dissolve 40 g
R1: Content
sodium hydroxide (NaOH) in 500 mL water
[ppm]
(Caution: solution gets hot!), add 65 g boric acid
1 144.574
(H3BO3), and fill up to 1000 mL with deionized
2 144.462
water.
3 144.356
4 144.216 The application method has been developed for
5 144.368 tap water. It may be necessary to optimize the
6 144.550 method for your sample.
Mean 144.421
Waste disposal
s 0.135
srel 0.093 % Neutralize with hydrochloric acid before final
The repeatability of the result is excellent with a disposal.
relative standard deviation below 0.1 %. Further information
Remarks http://www.mt.com/global/en/home/products/Labo
The method can be fully automatized using an ratory_Analytics_Browse/Product_Family_Browse_
InMotion™ sample changer. In such a case, titrators_main/Titration_Excellence.html
choose the appropriate sample changer in the
Titration stand method function.

Measured values
Volume dV/dt Potential 1st deriv. Time

[mL] [mL/s] [mV] [mV/mL] [s]
0 891.8 0
0.5 0.0795 868.7 6
0.51 0.001 876.9 14
0.52 0.003 877.8 18
0.53 0.004 878.5 20
0.54 0.003 878.4 33.15 24
0.55 0.004 878.1 -126.43 27
0.56 0.0035 877.5 -164.84 30
0.57 0.0035 876.6 -215.96 33
0.58 0.0035 871.5 -237.6 36
0.59 0.0035 869.4 -241.59 39
0.6 0.0035 867.8 -230.37 42
0.61 0.0035 866.2 -218.76 45
0.62 0.0035 863.5 -224.23 48
0.63 0.003 860.2 -313.38 51
0.64 0.003 856.4 -406.7 54
0.65 0.003 851.3 -425.11 57
0.66 0.003 843.8 -74.63 60
0.67 0.003 830.8 -1998.33 63
0.68 0.003 812.9 -5264.86 66
0.69 0.0025 780.8 -8139.88 70
0.7 0.002 705.6 -9535.74 75
0.703376 632.9 -9544.09 EQP
0.71 0.0005 490.3 -9039.4 88
0.72 0.001 427.8 -6824.13 99
0.73 0.003 422.4 -3592.86 102
0.74 0.003 418.4 -549.38 105

dV 0.01 mL
Method T5/T7/T9 Mode Equilibrium controlled
dE 2.0 mV
dt 1s
t (min) 3s
001 Title
t (max) 20 s
Type General titration Evaluation and recognition
Compatible with T5/T7/T9 Procedure Standard
ID M405 Threshold 1000 mV/mL
Title Total hardness of tap Tendency Negative
water Ranges 0
… Add. EQP criteria No
Termination
002 Sample At Vmax 10.0 mL
Number of IDs 1 At potential No
ID 1 Tap water At slope No
Entry type Fixed volume After number of recognized EQPs Yes
Volume 50 mL Number of EQPs 1
Density 1.0 g/mL Combined termination criteria No
Temperature 25.0°C 009 Calculation R1
Entry Arbitrary Result Content
Result unit ppm
003 Titration stand (Manual stand) Formula R1 = Q*C/(m*d)
Type Manual stand
M M[Calcium carbonate]
Titration stand Manual stand 1
z z[Calcium carbonate]
Decimal places 3
004 Dispense (normal) [1] Result limits No
Titrant ErioT solution Record statistics Yes
Concentration 1 Extra statistical func. No
Volume 1.0 mL Send to buffer No
Dosing rate 60 mL/min Condition No
005 Stir 010 Record

Speed 35 % Summary No
Duration 6s Results Per sample
Condition No Raw results Per sample
Table of meas. Values No
006 Dispense (normal) [2] Sample data No
Resource data No
Titrant 5 % NH3
E–V No
Concentration 1
dE/dV – V No
Volume 10.0 mL
log dE/dV –V No
d2E/dV2 – V No
BETA – V No
007 Stir E–t No
Speed 35 % V–t No
Duration 6s dV/dt – t No
Condition No T-t No
E – V & dE/dV – V No
008 Titration (EQP) [1] V – t & dV/dt – t No
Method No
Titrant
Series data No
Titrant EDTA
Condition No
Sensor
Type Phototrode 011 End of sample
Sensor DP5
Unit mV
Stir
Speed 35 %
Predispense
Mode volume
Volume 0.5 mL
Wait time 5s
Control
Control User
Titrant addition Incremental

Number of EQPs 1
Method G10S/G20S Combined termination criteria No
006 Calculation R1
Result type Predifined
001 Title Calculation type Direct titration
Type General titration Result Content
Compatible with G10S/G20S Result unit ppm
ID M405 Formula R1 = Q*C/(m*d)
Title Total hardness of tap Selected EQP 1
water Constant C = M*1000/z
… M M[Calcium carbonate]
z z[Calcium carbonate]
002 Sample Decimal places 3
Result limits No
Number of IDs 1
ID 1 Tap water
Entry type Fixed volume
Volume 50 mL
007 Record
Density 1.0 g/mL Summary No
Correction factor 1.0 Results Per sample
Temperature 25.0°C Raw results Per sample
Entry Arbitrary Table of meas. Values No
Sample data No
Resource data No
003 Titration stand (Manual stand)
E–V No
Type Manual stand
dE/dV – V No
Titration stand Manual stand 1
log dE/dV –V No
d2E/dV2 – V No
004 Stir BETA – V No
Speed 35 % E–t No
Duration 6s V–t No
Condition No dV/dt – t No
T-t No
005 Titration (EQP) [1] E – V & dE/dV – V No
V – t & dV/dt – t No
Titrant
Method No
Titrant EDTA
Series data No
Condition No
Sensor
Type Phototrode
Sensor DP5
008 End of sample
Unit mV
Stir
Speed 35 %
Predispense
Mode volume
Volume 0.5 mL
Wait time 5s
Control
Control User
Titrant addition Incremental
dV 0.01 mL
Mode Equilibrium controlled
dE 2.0 mV
dt 1s
t (min) 3s
t (max) 20 s
Procedure Standard
Threshold 1000 mV/mL
Tendency Negative
Ranges 0
Termination
At Vmax 10.0 mL
At potential No
At slope No


List of Standards
List of Standards
A lot of standards exist that describe analyses in the petroleum industry. In addition to the standards describing
titration methods, standards about other measurement techniques that can be performed with METTLER TOLEDO
instruments are listed here:
- Density
- Refractive index
- Dropping point
- UV/VIS
Density
Standard Description of test

ANSI 1250 Manual of Petroleum Measurement Standards
API Std 2540 Standard Guide for API Tables
ASTM D1250 Standard Guide for Use of the Petroleum Measurement Tables
ASTM D4052 Density of General Samples
ASTM D5002 Density of Crude Oil
ASTM D5931 Density of Engine Coolants
ASTM D7777 Density of General Samples by Portable Meter
DIN 51757 Density of Mineral Oils and Related Materials
EP, JP, USP Density using Oscillating U-Tube
IP 200/52 API Manual of Petroleum Measurement Standards
IP 365 Density of General Samples
IP 559 Density of Fuels by Portable Digital Meter
ISO 91 Petroleum Measurement Tables
ISO 12185 Density of Crude Oils and General Samples
ISO/EN 15212-1 Density using Oscillating U-Tube
Refractive index

ASTM D1218 Refractive index of General Products
ASTM D1747 Refractive Index of Viscous Materials
ASTM D2140 Viscosity Gravity Constant
ASTM D3321 Freezing Point Engine Coolants
ASTM D4542 Refractive Index of Soluble Salt of Soils
ASTM D5006 System Icing Inhibitors
DIN 51423 Refractive Index of Mineral Oils
UOP 816 Refractive Index of General Products

List of Standards
Dropping point
ASTM D566 Dropping Point of Lubricating Grease
ASTM D2265 Dropping Point of Lubricating Grease Over Wide Temperature Range
ASTM D3104 Softening Point of Pitches
ASTM D3461 Dropping Point of Asphalt/Bitumen
ASTM D3954 Dropping Point of Waxes, Polyolefins
DIN 51920 Softening Point of Binding and Impregnating Materials
DIN 51801 Dropping Point of Bitumen
DIN ISO 2176 Dropping Point of Petroleum Products and Lubricating Grease
IP 132 Dropping Point of Lubricating Grease
IP 396 Dropping Point of Lubricating Grease
UV/VIS
ASTM D1685 Traces of Thiophene in Benzene by Spectrophotometry
ASTM E1615 Iron in Trace Quantities Using the FerroZine Method
ASTM E819 Trace Amounts of Arsenic in Organic Industrial Chemicals
ASTM D2269 Evaluation of White Mineral Oils by Ultraviolet Absorption
ASTM D4046 Alkyl Nitrate in Diesel Fuels by Spectrophotometry
ASTM D1839 Amyl Nitrate in Diesel Fuels
ASTM E1784 Standard Test Method for Total Peroxides in Acrylonitrile
ASTM D4590 Colorimetric Determination of p-tert-Butylcaatechol in Styrene
Monomer
ASTM E533 Trace Amounts of Arsenic in Inorganic Industrial Chemicals
IP 298 Determination of quinizarin – Extraction spectrophotometric method
Titration
Titration: other methods
ASTM D94 Saponification Number of Petroleum Products
ASTM D1832 Peroxide Number of Wax
ASTM D2420 Hydrogen Sulfide Determination
ASTM D3703 Hydroperoxide Number of Fuels
ASTM D4929 Organic Chloride Content in Crude Oils
ASTM D6470 Salt in Crude Oils
ASTM E1899 Hydroxyl Number with TSI and TBAH Titration
DIN EN 51559 Saponification Number of Petroleum products
DIN EN 53240 Hydroxyl Number by Acetylation
UOP 269 Nitrogen Bases in Hydrocarbons
UOP 405 Hydrogen Chloride in Gas Streams
UOP 588 Total Inorganic and Organic Chloride in Hydrocarbons
UOP 729 Phenol in Light Distillates

List of Standards
Titration: Acid Number

ASTM D664 Acid Number by Potentiometric Titration
ASTM D8045 Acid Number by Thermometric Titration
ASTM D974 Acid Number by Colorimetric Titration
ASTM D3242 Acidity in Aviation Turbine Fuel
DIN EN 12634 Acid Number in Petroleum Products
IP 177 Acid Number in Petroleum Products
ISO 6619 Acid Number by Potentiometric Titration
UOP 565 Acid Number of Petroleum Products/Distillates
Titration: Base Number

ASTM D2896 Base Number by Perchloric Acid Titration
ASTM D4739 Base Number by Hydrochloric Acid Titration
ASTM D974 Base Number by Color Indicator Titration
DIN ISO 3771 Base Number by Hydrochloric Acid Titration
IP 139 Base Number by Color Indicator Titration
IP 276 Base Number by Perchloric Acid Titration
IP 417 Base Number by Potentiometric HCl Titration
Titration: Bromine Index, Bromine Number

ASTM D1159 Bromine Numbers of Distillates and Aliphatic Olefins
ASTM D1492 Bromine Index of Aromatic Hydrocarbons by Coulometric Titration
ASTM D2710 Bromine Index of Hydrocarbons
ASTM D5776 Bromine Index of Aromatic Hydrocarbons
IP 130 Bromine Number of Distillates and Aliphatic Olefins
ISO 3839 Bromine Number of Distillates and Aliphatic Olefins
UOP 304 Bromine Number and Index of Hydrocarbons
Titration: Mercaptan
ASTM D3227 Thiol (mercaptan) Sulfur in Light Distillates
IP 342 Thiol (mercaptan) Sulfur in Distillates
ISO 3012 Thiol (mercaptan) Sulfur in Distillates
UOP 163 Hydrogen Sulfide and Mercaptan Sulfur in Liquid Hydrocarbons
UOP 212 Hydrogen Sulfide, Mercaptan Sulfur, and Carbonyl Sulfide in
Hydrocarbon Gases

List of Standards
Titration: Water determination
DIN 51777 Water in Solvents/Hydrocarbons (Volumetric
and Coulometric)
Coulometric Determination
ASTM D6304 Water in Petroleum Products
ASTM E1064 Water in Organic Liquids
ISO 12937 Water in Petroleum Products
UOP 481 Water in Liquid Hydrocarbons
Volumetric Determination
ASTM D1364 Water in Volatile Solvents
ASTM E203 Water in General Samples
IP 471 Water in Distillates
Titration: Refinery Processes

ASTM D512 Chloride in Water
M,ASTM D513 Carbon Dioxide in Water
ASTM D888 Total Dissolved Oxygen in Water
ASTM D1067 Acidity and Alkalinity in Water
ASTM D1125 Conductivity in Water
ASTM D1179 Fluoride in Water
ASTM D1252 Chemical Oxygen Demand of Water
ASTM D1293 pH Measurement of Water
ISO 10523 pH Measurement of Water
ASTM D1426 Ammonia by ISE Measurement in Water
ASTM D2036 Cyanide in Water (ISE Measurement and Titration)
DIN 38409 p- and m-Values (Acidity and Alkalinity) in Water
UOP 209 Alkalinity, Sulfide and Mercaptide in Refinery
Caustics
UOP 423 Thiosulfate in Refinery Caustics
UOP 456 Chloride in Refinery Waters
UOP 975 Fluorine in LPG by ISE

The Perfect Match
For Every Purpose
Density & Refractometry

The multitalented LiquiPhysics system reliably measures
density, refractive index and related values such as °Brix, HFCS,
alcohol concentrations or API gravity. It can be automated and
upgraded to multiparameter systems for simultaneous determi-
nation of additional parameters such as pH / conductivity, color,
acidity and more.
Titration Excellence
The intuitive user interface and One Click operation make
titrations and manual operations fast and simple on your
Excellence Titrators. Secure your analyses with detailed user
management, Plug & Play sensors, burettes and peripherals.
Build the titrator for your needs today and tomorrow, with our
multitude of modular accessories.
UV/VIS Spectrophotometers
The new UV / VIS Excellence spectrophotometers from
METTLER TOLEDO optimize spectroscopic workflows. FastTrack™
Technology makes for speedy and reliable measurements with in
a very compact footprint. Trustworthy performance is combined
with intuitive and efficient One Click operation for a wide range
of applications.
Melting Point & Dropping Point

Multiple methods such as melting, boiling, cloud, slip melting,
dropping and softening point can be used to characterize
a substance and analyze its properties. METTLER TOLEDO‘s
Melting Point and Dropping Point Excellence Systems offer the
possibility of measuring these thermal values accurately,
automatically, and with compliance to international standards.
www.mt.com/Titration-Excellence
For more information
Mettler-Toledo GmbH, Analytical

Sonnenbergstrasse 74
CH-8606 Schwerzenbach, Switzerland
Tel. +41-44 806 77 11
Fax +41-44 806 73 50
Subject to technical changes

© 11/2017 Mettler-Toledo GmbH, 30418770
Markt Support AnaChem

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Book 20%

METTLER TOLEDO Application Brochure 48

Figure 1: Modularity of Titration Excellence instruments

Daniel Buchmann Dr. Nicolas Monney

METTLER TOLEDO Application Brochure 48

METTLER TOLEDO Application Brochure 48

ACID NUMBER DETERMINATION ...................................................................................... 3

Automated Acid Number Determination according to ASTM D664-11a .......................................................... 4

BASE NUMBER DETERMINATION ....................................................................................23

Automated Base Number Determination according to ASTM D4739 ............................................................. 24

Base Number Determination in Oil by Thermometric Titration ..................................................................... 30

BROMINE INDEX AND BROMINE NUMBER .......................................................................43

Bromine Index Determination According to ASTM D1492 (5 mA) ................................................................ 44

Automated Bromine Number Determination of Petrol According to ASTM D1159-01 .................................... 50

WATER CONTENT ..........................................................................................................67

Water Content of a Lubricant with InMotion KF ........................................................................................... 68

Automated Water Content Determination of Brake Fluid with InMotion KF .................................................... 74

REFINERY PROCESSES ..................................................................................................81

Total Hardness of Tap Water by Photometric Titration ................................................................................. 82

LIST OF STANDARDS .....................................................................................................88

METTLER TOLEDO Application Brochure 48

METTLER TOLEDO Page 2 of 91

Standard Description of test Mettler-Toledo Titration methods

1. Potentiometric method according to ASTM D664, M726

2. Thermometric method according to ASTM D8045, M721

METTLER TOLEDO Page 3 of 91

Automated Acid Number Determination

METTLER TOLEDO Page 4 of 91

 Titration Excellence T7 (30252675) or Remarks

METTLER TOLEDO Page 5 of 91

METTLER TOLEDO Page 6 of 91

1.2345 0.0025 -219.2 -467.14 178 21.4

METTLER TOLEDO Page 7 of 91

METTLER TOLEDO Page 8 of 91

METTLER TOLEDO Page 9 of 91

023 End of sample

METTLER TOLEDO Page 10 of 91

METTLER TOLEDO Page 11 of 91

Acid Number in Crude Oil by Thermometric

paraformaldehyde plays the role of thermometric

METTLER TOLEDO Page 12 of 91

 Titration Excellence T5 (30252672) T7

METTLER TOLEDO Page 13 of 91

Waste disposal and safety measures Further information

Thermometric acid number, sample 2/7

Volume Meas. value Change 2nd deriv. Time

METTLER TOLEDO Page 14 of 91

004 Pump 009 Conditioning

METTLER TOLEDO Page 15 of 91

Acid Number in Crude Oil by Thermometric

1 g of sample, expressed as mg KOH/g.

METTLER TOLEDO Page 16 of 91

Chemistry R5: Titer 1.003

 Conductivity board (51109840) with FW

In the Titration (Therm.) method function, a

The maximal volume of a thermometric titration is

Suspending the measurement during titration may

METTLER TOLEDO Page 17 of 91

Titer and blank measurement: 𝑛𝑇𝑂𝑇) ∗ 𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗ 𝑝𝑤(𝑛 − 𝑛𝑇𝑂𝑇) ∗

The part of the calculation with “pw(n-nTOT)”

The blank value, is calculated as follow:

METTLER TOLEDO Page 18 of 91

Thermometric acid number, sample 1/4