METTLER TOLEDO Application M242

Determination of the Amine Value

Determination of the amine value by non-aqueous titration in glacial acetic acid with perchloric acid.

Sample MOCA (4,4'-Diamino-3,3'- Preparation and Procedures

dichlorodiphenylmethane)
1) The amount of sample used depends on the
expected amine number.
2) The recommended volume used for the titration
Compound Amine groups in polymers and
should be between 30% and 70% of the total
polymer raw materials / building
burette volume.
blocks.
Sensor cleaning:

Chemicals 60 mL glacial acetic acid 1) Rinse the sensor after each titration with glacial
acetic acid (or a stronger solvent like e.g. acetone,
if necessary).
2) Condition the sensor in water for at least 2
minutes to rehydrate the pH membrane of the
Titrant Perchloric acid (HClO4) in electrode.
glacial acetic acid. 3) Rinse the electrode with glacial acetic acid
C(HClO4) = 0.1 mol/L before going to the next sample to remove of all the
water.
Water is a stronger base than glacial acetic acid
Standard TRIS / THAM (IUPAC: 2-Amino- and would interfere with the titration; therefore its
2-hydroxymethyl-propane-1,3- presence should be avoided.
diol)

Indication DG113-SC
Remarks
A blank value for the solvent is usually not required,
Chemistry HClO4 + CH3COOH ⇌ if it is, a blank value like e.g. B[Amine Value] as
+ -
CH3COOH2 + ClO4 (titrant) given in the calculation should be used. If no blank
MOCA + CH3COOH2 ⇌ value is required, B[Amine Value] can be omitted
+

+
MOCA-H + CH3COOH (sample from the calculation.
titration)
When used for amine value determination of
Calculation Amine value in mg KOH/g: polyurethane raw materials, this application can be
R = (Q-B[Amine Value])*C/m used as a basis for compliance with ASTM D6979-
C = M/z 03 or ISO 25761.

+
B[Amine Value] = blank value The CH3COOH2 ions created in the titrant
solvent. composed of perchloric acid in glacial acetic acid,
are very strong proton donors to normally weak
bases, therefore the titrant works as an extremely
strong acid solution.
Waste Organic solvent waste.
disposal MOCA is harmful for the With a weak base like an amine this means that the
environment. solvent / titrant combination enhances the alkaline
properties of the amine. This makes it possible to
titrate the amine solution and get a sharp endpoint
Author, Melanie Nijman, v2.0
which would not be possible in aqueous solutions.
Version

METTLER TOLEDO Page 1 of 4 Titration Application M242

 Instruments Titration Excellence T70/T90
Rondo 20 Sample Changer
1 additional dosing unit (20 mL)

Accessories DV1010 and DV1020 Burettes

1 SP250 peristaltic pump ME-51108016
Titration beakers ME-101974
LabX titration software

Results
All results
Method-ID m242-08
Sample MOCA (1/6)
R1 (Amine value) 410.07197 mg KOH/g
Sample MOCA (2/6)
R1 (Amine value) 413.07536 mg KOH/g
Sample MOCA (3/6)
R1 (Amine value) 412.40496 mg KOH/g
Sample MOCA (4/6)
R1 (Amine value) 413.25155 mg KOH/g
Sample MOCA (5/6)
R1 (Amine value) 413.93275 mg KOH/g
Sample MOCA (6/6)
R1 (Amine value) 411.56977 mg KOH/g

Statistics
Method-ID m242-08
R1 Amine value (mg KOH/g)
Samples n=6
Mean 412.38439
s 1.388390
srel 0.337%

Titration curve

METTLER TOLEDO Page 2 of 4 Titration Application M242

 Table of measured values
Volume [mL] Increment [mL] Signal [mV] Change [mV] 1st deriv. [mV/mL] Time [s] Temperature [°C]
0 NaN 452.7 NaN NaN 0 25
0.010 0.010 453.8 1.1 NaN 5 25
0.020 0.010 455.2 1.4 NaN 10 25
0.045 0.025 458.3 3.1 NaN 15 25
0.098 0.053 463.5 5.2 NaN 20 25
0.173 0.075 469.1 5.6 72.19 25 25
0.281 0.108 475.2 6.1 56.62 30 25
0.424 0.143 481.3 6.1 44.01 36 25
0.608 0.184 487.4 6.1 34.18 41 25
0.839 0.231 493.5 6.1 26.94 46 25
1.123 0.284 500.0 6.5 22.24 51 25
1.424 0.301 506.2 6.2 19.64 56 25
1.752 0.328 512.2 6.0 18.28 61 25
2.118 0.366 518.9 6.7 17.72 66 25
2.450 0.332 524.8 5.9 17.75 71 25
2.796 0.346 531.0 6.2 18.20 76 25
3.124 0.328 537.2 6.2 19.01 81 25
3.432 0.308 543.2 6.0 20.02 86 25
3.726 0.294 549.2 6.0 21.49 92 25
4.004 0.278 555.4 6.2 23.42 96 25
4.254 0.250 561.5 6.1 25.84 102 25
4.481 0.227 567.5 6.0 29.07 107 25
4.684 0.203 573.7 6.2 33.10 112 25
4.858 0.174 579.6 5.9 37.84 117 25
5.016 0.158 585.8 6.2 43.87 122 25
5.148 0.132 592.0 6.2 50.69 127 25
5.258 0.110 597.7 5.7 58.01 132 25
5.360 0.102 603.8 6.1 66.82 137 25
5.446 0.086 610.0 6.2 75.75 142 25
5.517 0.071 615.7 5.7 84.34 147 25
5.585 0.068 621.8 6.1 93.45 152 25
5.643 0.058 627.6 5.8 100.40 158 25
5.697 0.054 633.3 5.7 104.42 162 25
EQP1 5.718689 NaN 635.6 NaN 104.71 NaN NaN
5.752 0.055 639.2 5.9 104.24 168 25
5.808 0.056 645.0 5.8 97.97 173 25
5.866 0.058 650.7 5.7 88.90 178 25
5.932 0.066 656.4 5.7 78.89 183 25
6.008 0.076 662.2 5.8 68.93 188 25
6.102 0.094 667.8 5.6 NaN 193 25
6.223 0.121 673.9 6.1 NaN 198 25
6.370 0.147 679.6 5.7 NaN 203 25
6.566 0.196 685.5 5.9 NaN 208 25
6.827 0.261 691.7 6.2 NaN 213 25

Comments
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METTLER TOLEDO Page 3 of 4 Titration Application M242

 Method
001 Title Accompanying stating
Type General titration Accompanying stating No
Compatible with T70 / T90 Condition
ID m242-08 Condition No
Title Amine value
Author Administrator 008 Rinse
Date/Time 19.05.2008 08:27:11 Auxiliary reagent Acetic acid
Modified at 22.05.2008 08:06:27 Rinse cycles 1
Modified by Administrator Vol. per cycle [mL] 15
Protect No Position Actual position
SOP None Drain Yes
Drain pump SP250
002 Sample Condition No
Number of IDs 1
ID 1 MOCA 009 Calculation R1
Entry type Weight Result Amine value
Lower limit [g] 0.0 Result unit mg KOH/g
Upper limit [g] 5.0 Formula R1=(Q-B[Amine Value])*C/m
Density [g/mL] 1.0 Constant C=M/z
Correction factor 1.0 M M[Potassium hydroxide]
Temperature [°C] 25.0 z z[Potassium hydroxide]
Entry Before Decimal places 5
Result limits No
003 Titration stand (Rondo/Tower A) Record statistics Yes
Type Rondo/Tower A Extra statistical func. No
Titration stand Rondo60/1A Send to buffer No
Lid handling No Condition No

004 Rinse 010 Conditioning

Auxiliary reagent Acetic acid Type Fix
Rinse cycles 1 Interval 1
Vol. per cycle [mL] 15 Position Conditioning beaker
Position Rinse beaker Time [s] 120
Drain Yes Speed [%] 30
Drain pump SP250 Condition No
Condition No
011 End of sample
005 Dispense (normal) [1]
Titrant Acetic acid
Concentration 100
Volume [mL] 60
Dosing rate [mL/min] 60.0
Condition No

006 Stir
Speed [50%] 50
Duration [s] 330
Condition No

007 Titration (EQP) [1]

Titrant
Titrant HClO4
Concentration [mol/L] 0.1
Sensor
Type pH
Sensor DG113-SC
Unit mV
Temperatur acquisition
Temperature measurement No
Stir
Speed [%] 50
Predispense
Mode None
Waiting time [s] 0
Control
Control User
Titrant addition Dynamic
dE (set value) [mV] 6.0
dV (min) [mL] 0.01
dV (max) [mL] 0.5
Mode Equilibrium controlled
dE [mV] 0.5
dt [s] 2
t (min) [s] 5
t (max) [s] 30
Evaluation and recognition
Procedure Standard
Threshold [mV/mL] 30
Tendency None
Ranges 0
Add. EQP criteria No
Termination
At Vmax [mL] 12.0
At potential No
At slope No
After number of recognized EQPs Yes
Number of EQPs 1
Combined termination criteria No

METTLER TOLEDO Page 4 of 4 Titration Application M242