METTLER TOLEDO

M084

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

The acid number is the amount of potassium hydroxide used to neutralized acidic components in different samples (mg KOH/g). Here the determination of the acid value according to DIN 53402 (1973) is presented. Sample
Organic solvents, resins, oils, fats fatty acids, softeners, polymers

Preparation and Procedures

Solvent mixture according to DIN 53402 (1973): Toluene:ethanol 2:1 Hints: 1) Ensure good stirring. Speed and stirring time can be adapted according to the viscosity or the bad solubility of the sample. 2) If the dissolution of the sample is not straightforward, heating my be applied to improve it. Ultrasonics can also be applied. 3) The titration can also indicated photometrically by a phototrode and a color indicator. It can be affected by the limitations of the indicators, by the formation of precipitates, or by change in turbidity. 4) Use the same amount of solvent mixture for the blank as well as for the sample determination. 5) Substances which undergo side reactions with the alkaline titrant can not be titrated.

Substance Chemicals

Acidic components

40 mL solvent mixture: Toluene:ethanol 2:1

Titrant

KOH in Ethanol: c(KOH) = 0.1 mol/L, c(KOH) = 0.01 mol/L Potassium hydrogen phthalate DL50Graphix, DL53/55/58 DL70ES, DL77

Standard Instruments

Accessories

1 additional burette DV1005, 1 additional burette DV1020 100 mL titration beaker ME-101974 AT261 balance, Printer DG113-SC

Remarks
This application describes the determination of the acid value of resins, oils, fats, fatty acids, solvents, softeners, polymers and other technical organic products. Due to better solubility properties, this kind of titration is often carried out in a binary solvent mixture. The titrant is dissolved in a solvent wich is miscible with the solvent mixture, i.e. in ethanol or methanol. If needed, an auxiliary solvent like acetone can be added to improve solubility. The whole acidic components are neutralized, including half of the acid anhydride. Since the content of free anhydride is small, this error can be generally neglected. On the other hand, if significant amounts of anhydride are present, an additional titration with aqueous potassium hydroxide solution must be performed to determine the second missing half anhydride.

Indication Chemistry

OH- + H+ = H2O

Calculation

Blank determination (Meth. 084B): R1 = Q R1 is stored as aux. value H8 Acid value determination (Meth: 084A): R1 = (Q1 - H8)*C1/m ; C1 = 56.1

Results

Waste disposal

Organic solvent waste (chlorinated and not chlorinated)

Literature: DIN 53402, 51588 ISO 3682

Author

Kees Mooibroek

Results
Method 084A Acid Values, Solvent Blank 13-Apr-1994 User K.M. Measured 13-Apr-1994 11:09 RESULTS No ID1 ID2 Sample amount and results 1/1 Solv.Bl. Blank 40.0 g Weight m R1 = 0.006 mmol Blank Acid No 1/2 Solv.Bl. Blank 40.0 g Weight m R1 = 0.005 mmol Blank Acid No 1/3 Solv.Bl. Blank 40.0 g Weight m R1 = 0.005 mmol Blank Acid No 1/4 Solv.Bl. Blank 40.0 g Weight m R1 = 0.001 mmol Blank Acid No STATISTICS Number results R1 Mean value Standard deviation Rel. standard deviation Outlier test : sample No. Number results R1 Mean value Standard deviation Rel. standard deviation AUXILIARY VALUE New value Method User Measured n x s srel n x s srel H8 = = = = = = = = 4 0.004 0.002337 59.191 1/4 3 0.004 0.000592 11.626 10:38

mmol mmol % mmol mmol %

Blank Acid No Blank Acid No

Blank Acid No Blank Acid No

= 0.005091

Blank Acid No 15-Apr-1994 14:35

084B Acid Values (non aqueous) K.M. 15-Apr-1994 16:18

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

Table of measured values

Titration curve

Method
Method 084B Version Acid values (non aqueous) 15-Apr-1994 14:35 Method 084A Version Acid Values, Solvent Blank 13-Apr-1994 10:38 Title Method ID . . . . . . . . . . . . . 084B Title . . . . . . . . . . . . . . . Acid values (non aqueous) Date/time . . . . . . . . . . . . . 15-Apr-1994 14:35 Sample Number samples . . . . . . . . . . . 7 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . Acid val Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . Manual Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60 Titration Titrant . . . . . . . . . . . . . . KOH (Isoprop.) Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 500 EQP range . . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . +500 Limit B [mV, pH,...] . . . . . -500 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure. . . . . . . Standard Calculation Result name . . . . . . . . . . . . Acid Value Formula . . . . . . . . . . . . . . R1=(Q1-H8)*C1/m Constant . . . . . . . . . . . . . . C1=56.1 Result unit . . . . . . . . . . . . mg KOH/g Decimal places . . . . . . . . . . . 3 Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . Yes Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes Title Method ID . . . . . . . . . . . . . 084A Title . . . . . . . . . . . . . . . Acid Values, Solvent Blank Date/time . . . . . . . . . . . . . 13-Apr-1994 10:38 Sample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [g] . . . . . . . . . 50.0 ID1 . . . . . . . . . . . . . . . . SolvBl. Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1 Temperatur sensor . . . . . . . . . Manual Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 60 Titration Titrant . . . . . . . . . . . . . . KOH (Isoprop.) Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG113-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.02 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 500 EQP range . . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . +500 Limit B [mV, pH,...] . . . . . -500 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure. . . . . . . Standard Calculation Result name . . . . . . . . . . . . Blank Acid No Formula . . . . . . . . . . . . . . R1=Q Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 3 Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . Yes Auxiliary value ID text . . . . . . . . . . . . . . Blank Acid No. Formula . . . . . . . . . . . . . . H8=x Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes