Procedure for Acid Number of Petroleum Products by Potentiometric Titration

(ASTM D664-18)

Instrument

1. Check the desiccant trap for the titrant. The desiccant should be blue when dry. If the
desiccant is pink or purple replace it with dried desiccant.
2. Press the red [STOP/POWER] key to power on the instrument
3. The instrument will prompt the user to carry out the PREP function for the burette, select
ok.

Preparation of electrodes

1. Rinse the electrode with the titration solvent, isopropanol then distilled water.
2. Dip the electrode into pH 4 aqueous buffer solution, and record the mV value after 1
min.
3. Dip the electrode into pH 7 aqueous buffer, and record the mV value after 1 min.
4. Calculate the mV difference. The difference should be ≥ 162mV at 20-25 oC. If the
difference is less than 162mV, clean or replace the electrode.

5. Soak the electrodes in water (pH 4.5-5.5) for at least 5 min. rinse with anhydrous
isopropanol then with titration solvent.
6. Immerse the electrode in the pH 10 buffer while stirring for 5 min and record the mV
readings. The temperature of the buffer solution should be within 2 oC of the sample
temperature. This reading is to be used as titration end point where no inflection is
detected.

Blank Titration
1. At the main menu select method, DET_U-Blank. Load the method.
2. In a 250mL beaker add 125mL or 60mL of titration solvent depending on the volume of
solvent to be used for sample analysis. The same volume of titration solvent must be
used for the blank and sample. See Table 1
3. A graph of mV vs mL of KOH will be plotted in real time
4. Allow the titration to continue to the final inflection point detected.

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 5. Record the volume of titrant used at the final inflection point. This value will be used as
the inflection end point.
6. If no inflection point is detected, allow the titration to continue for 30min before
manually stopping.
7. From the titration curve find the mV reading matching the mV reading of the pH 10
buffer solution and record the corresponding titer volume. This will be used as the
buffer endpoint.
8. Rinse with titration solvent, isopropanol and water. Leave the electrode immersed in
water for at least 5 min, then rinse with isopropanol and titration solvent before
proceeding to another titration.

Table 1: Recommended size of test portion

Acid Number Accuracy of Mass of sample for Mass of sample for

weighing (g) 125mL of solvent 60mL of solvent
0.05 - <0.10 0.10 20.0 ± 2.0 10.0 ± 1.0
1.0 - < 5.0 0.02 5.0 ± 0.5 2.5 ± 0.25
5 - < 20.0 0.005 1.0 ± 0.1 0.5 ± 0.05
20 - < 100 0.001 0.25 ± 0.02 0.25 ±0.02
100 - < 260 0.0005 0.1 ± 0.01 0.1 ± 0.01

Standardization of 0.1M KOH Titrant

1. Dry 15g of Potassium Hydrogen Phthalate (KHP) at 120 oC for 2 hours.

2. Cool in a desiccator, weigh 10g ± 0.0001g of dried KHP and dissolve in 500mL of CO 2
free water
3. Pipette 2mL of the KHP solution into a 250mL beaker and add 50mL of CO 2 free water.
4. From the main menu, select method and load the DET_U-Titer method
5. Lower the electrode and stirrer into the liquid. The electrode tip should be submerged
approximately 2.5cm below the surface of the liquid.
6. Titrate to the first inflection point and record the titrant volume used.
7. Prepare two additional KHP solutions to standardize the titrant in triplicate.
8. Use the average of the three titer volumes for standardization.

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Sample Titration

1. At the main menu select method and load the DET_U-Sample method.
2. In a 250mL beaker weigh an appropriate mass of sample based on the expected acid
number and add the required volume of solvent. See Table 1
3. Enter the sample number and mass used in the instrument,
4. Lower the electrode and stirrer into the liquid. The electrode tip should be submerged
approximately 2.5cm below the surface of the liquid, then press [START].
5. A live graph of mV vs mL of KOH will be plotted.
6. Allow the titration to continue to the final inflection point detected.
7. Record the volume of titrant used at the final inflection point. This value will be used as
the inflection end point.
8. If no inflection point is detected, the titration can be manually ended when the mV
signal reaches the pH 10 buffer potential.
9. From the titration curve find the mV reading closest to the mV reading of the pH 10
buffer solution and record the corresponding titer volume. This will be used as the
buffer endpoint
10. Rinse with titration solvent, isopropanol and water. Leave the electrode immersed in
water for at least 5 min, then rinse with isopropanol and titration solvent before
proceeding to another titration.

Strong Acid Number Titration

For strong acid number, carry out both the blank and sample titrations to an end point
occurring at the pH 4 buffer mV reading.

Calculations

KHP solution molarity (mol/L) = mass of KHP (g)

204.23 × volume of KHP solution (L)

KOH molarity (mol/L) = 2.0 mL KHP × KHP conc

Volume of KOH used (mL)

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Acid number (mg KOH/g) = (KOH titer volume – Blank volume) × KOH conc × 56.1
Mass of sample (g)

Strong acid number (mg KOH/g) = (CM + Dm) × 56.1

Mass of sample (g)

C = Volume of KOH used to reach pH 4 buffer mV (mL)

M = KOH concentration (mol/L)
D = Alcoholic HCL used to titrate blank to end point corresponding to C (mL)
m = concentration of alcoholic HCL (mol/L)

Report
Report the results for acid number or strong acid number to the nearest 0.01 as mg KOH/g of
sample as well as the type of endpoint used: inflection point or buffer endpoint. Report the
sample size used if it differs from the recommended sample size in Table 1.

Repeatability & Reproducibility

Repeatability = 0.0264 × A0.4 mg/kg KOH

Reproducibility = 0.177 × A0.4 mg/kg KOH