Bromine Number of Petroleum Products

(ASTM D1159-98 Electrometric titration)

Introduction Carefully mix one volume of concentrated sulphuric

This method covers bromine number determination of acid with 5 volumes of distilled water. Caution: the
certain petroleum products indicated in ASTM standard dilution reaction is exothermic.
D1159-98. The magnitude of the bromine number is
Titration solvent (see notes)
simply an indication of the bromine reactive
constituents, not an indication of the constituents. The Mix 714 ml of glacial acetic acid (CH3COOH), 134 ml of
bromine number mainly indicates the concentration of dichloromethane (CH2Cl2), 134 ml of methanol (CH3OH)
double bonds present in the product. and 18 ml of sulphuric acid (1+5).
Principle Dichloromethane (CH2Cl2)
Expressed as g of Bromine (Br2) able to react with 100
g of product, the bromine number determination uses Warning: Reagents used in this application note are
the reaction between a (Br-/BrO3-) solution and the flammable. They can cause severe burns and are
hazardous if swallowed, breathed or come into contact
petroleum product according to the following reactions
with the skin or eyes. Always respect laboratory health
a) 5 Br- + BrO3 - + 6H+ .. 3Br2 + 3H2O and safety regulations when using these reagents.
b) Br2 + R-C=C-R
R-C-C-R Infletion Detection settings
|| CONTINUOUS IP
Br-Br Titration with blank
(main reaction with product) Burette volume: 10 ml (see notes)
Max. volume: 7 ml
(Note that other reactions can occur such as addition, Stirring speed: 500 rpm
substitution or oxidation) Working mode: mV with i >0
To avoid secondary reactions the titration is run at low Current: DC
temperature (close to 5°C). Current value: 5µA (see notes)
Blank: YES
The titrant concentration, expressed as Br2 Start timer: 30 s
concentration, is 0.25 mol/l (or ¼ mol/l). According to Stop point: 0 mV
reaction (a), the titrant contains 5/12 mole of KBr and
1/12 mol/l of KBrO3.The molar weight of KBr is 119.9 Minimum speed: 0.50 ml/min
Maximum speed: 2.00 ml/min
g/mol and for KBrO3 167.9 g/mol. Titration is run
Smoothing param: 8
according to an inflection determination with imposed
current potentiometry and a double platinum wire Titration: Decreasing potential
electrode. Inflection number: 1
Stop at last IP: YES
Electrode and reagents
M241Pt2-8 Metal Electrode, double platinum (part no. Inflection 1:
E32M002) or M231Pt2 Metal Electrode, double Min. ordinate: 200 mV
platinum (part no. E32M001) with adapter part no. Max. ordinate: 800 mV
A94P801 T201 Temperature sensor (part no. E51M001)
Sample
Water-jacketed titration beaker connected to a low
Dilution: YES
temperature thermostat or a bath filled with ice
Sample unit: g
Bromide-Bromate titrant solution (0.25 mol/l as
Sample amount: 2
bromine concentration)
(see working range)
Dissolve 51.0 g of KBr (5*119.9/12) and 13.92 g of Final dilution vol.: 50 ml
KBrO3 (167.01/12) in 1000 ml of distilled water using Aliquot: 5 ml
a volumetric flask. (see working range)
Sulphuric acid (1+5)
 Result 1: ml Working range
For a sample amount of 1g, and a calculated dilution
Equation 1:
coefficient of 10 (50 ml for final dilution volume and
Equation Unit: Bromine number
5 ml for the aliquot), 1 ml of 0.25 mol/l titrant
Equation:
corresponds to a Bromine number of 37.5.
(R1*CT*15.98*DA/(SA*AL)
(see notes) The magnitude of the bromine number of a sample is
often unknown and it is necessary to perform a
Procedure
preliminary test with 2 g of sample.
Connect the double platinum wire electrode to the
corresponding input of the Titration Manager. ASTM Standard D1159 gives a table for sample amount
as a function of Bromine number:
Connect the temperature sensor to the corresponding
Bromine number Sample amount in g Titrant volume in ml
input on the Titration Manager.
0-10 20-16 Around 4
For a new titration solvent batch run a BLANK titration 10-20 10-8 Around 3-4
with 115 ml of titration solvent and 5 ml of 20-50 5-4 Around 5
dichloromethane. The experimental blank volume is 50-100 2-1.5 Around 4
100-150 1.6-0.8 Around 3-4
generally lower than 0.1 ml.
150-200 0.8-0.6 Around 3-4
Sample preparation
Place 10 ml of dichloromethane in a 50 ml volumetric
Notes
flask then add the weighed sample and fill the flask to
Notes regarding the titration solvent
the mark with dichloromethane.
ASTM Standard D1159 gives trichloroethane as an
Add 110 ml of titration solvent to the titration beaker. alternative for dichloromethane. However, the use of
this solvent is forbidden in many countries. To save
Add an aliquot (generally 5 ml but not more than 10
time, you can store the titration solvent in a
ml) of the sample solution in dichloromethane.
refrigerator between the experiments.
Dip the electrode, temperature sensor and delivery tip
Note regarding the maximum volume
in the beaker and immerse the beaker in an ice bath or
To avoid a two-phase system during titration, it is not
alternatively in a low temperature thermostatic bath.
recommended to use a titrant volume higher than 10
Using the electrode direct measurement function of the ml.
Titration Manager (icon ELECTRODES and
Note regarding the imposed current
"DISPLAY MEASUREMENT) allow the solution to reach
A 1 µA imposed current can give noisy curves and 10
the mentioned temperature (around 5°C) (see notes).
µA gives a curve that is not well defined around the
Run the titration. inflection point. Instead of DC imposed current it is
possible to use AC imposed current. A 25 µA AC
Results imposed current gives titration curves similar to those
As indicated above, results are expressed in g of Br2 obtained with 5 µA DC current. In this case, also
able to react with 100 g of product. modify the "Br- Nb-Ctrl-Temp" method.
R(bromine number) = Note regarding the equation
(Vtitr- Vblk)*C(titr)*159.8*100/ W(smp)*1000 The entered equation takes into account the
Vtitr = Total volume of titrant used in ml programmed dilution of the sample. DA is the final
dilution volume and AL the aliquot volume.
Vblk = Blank volume used for solvent titration
Note regarding sample handling
C (titr) = Concentration of titrant in mol/l For sample and dichloromethane handling, you can
W (smp) = Sample weight in g use a glass syringe instead of a pipette.
159.8 = molecular weight of Br2 Note regarding temperature measurement
As indicated previously, you can use the DISPLAY
100 = conversion factor for 100 g of product MEASUREMENT function, but in this case you can
1000 = correction factor for result in g instead of mg just check the temperature of the solution (DISPLAY
MEASUREMENT checks the measured potential on
For 5 determinations on cyclohexene (C6H10) E1 and E2 inputs, not on Pt-Pt input). You can use this
Mean delivered volume: 3.42 ml information in the pre-programmed method "Br- Nb-
Rel. standard deviation: 1.2% Ctrl-Temp" that measures the potential of the double
Corresp. Bromine number: 193 platinum wire electrode AND the sample temperature.
Theoretical: 194.6
Note regarding the curve shape
Based on experience, the starting potential may be
around 1300 mV and suddenly falls to around 800 mV
at the beginning of the titration. Then the curve falls
very quickly to the final measured potential (generally
around 100 mV) near the inflection point.
Curve