Title: Determination of Free Fatty Acids and Acid Value in Fats and Oils

Objectives: To determine the free fatty acid content and acid value in fats and oils
Introduction:
In this experiment, two parameters which are the percentage of free fatty acids and acid value in
palm oil were determined by acid-base titration method. The fatty acid (RCOOH) present in palm oil
is palmitic acid.
The acid value is defined as the weight of KOH in mg needed to neutralize the organic acids present
in 1g of fat and it is a measure of the free fatty acids (FFA) present in the fat or oil (Vitz et al.,
2019). FFA% is the weight to weight ratio of FFA found in an oil sample (Tech, 2019).
The oil is dissolved in an organic solvent which is ethanol in this experiment. Although weakly
acidic, ethanol is neutralized with alkali beforehand. This is to ensure that the determination of free
fatty acids is not interfered, and the neutral solvents aids in determining the free fatty acids present in
the oil sample. If the ethanol is not neutralised beforehand, it may consume more sodium hydroxide,
leading to wrong determination of free fatty acid.
Lastly, the solution is titrated with potassium hydroxide, KOH. As free fatty acids are weak acids
whereas potassium hydroxide (KOH) is a strong base, a suitable indicator, phenolphthalein is used
for the titration (Vitz et al., 2019). The titration is carried out until the solution turns pink, indicating
that the endpoint is reached.
During titration, the fatty acid (carboxylic acid) turns to its conjugate base (carboxylate), in which
the carboxyl group (-COOH ) becomes carboxylate ion (-COO-), with the reaction shown as follows:

R-COOH + KOH → R-COO- + K+ + H2O (Mettler Toledo, n.d.).

Procedure:
1. 5g of palm oil sample was accurately weighed ad transferred into a 250-mL Erlenmeyer flask.
2. 100mL of neutralized ethanol and a few drops of phenolphthalein indicator were added.
3. The mixture was shaken to dissolve completely.
4. The mixture was titrated with 0.1N NaOH, and was shaken until the endpoint is reached, which
was indicated by a slight pink colour that persisted for 30 seconds.
5. The volume of titrant used was recorded.
6. Steps 1-5 were repeated carefully in triplicate, each weight of the sample and the volume of titrant
were recorded.
Precaution steps:
1. The weight of the palm oil sample was accurately recorded to give precise calculations.
2. Two clamps were used to clamp the burette on the retort stand to increase the stability of the
burette.
3. The titrant must be released one drop by one drop to prevent overtitrating for increased accuracy.
4. The procedure was repeated in triplicate for increased accuracy.
Results & Calculation:
Table 1 shows the titration result obtained:
Palm Oil Sample Mass of Palm Oil (g) Volume of 0.1N KOH used (mL)
1 5.00 3.6
2 5.03 3.6
3 5.01 3.6

As palm oil was used in this practical, the FFA% is calculated using the expression below:
25.6  N  V
FFA% as palmitic acid (for palm oil and fractions) 
W
Where
Value of 25.6 is the formula for FFA determination is equivalence factors for palmitic acid; the
predominant fatty acid in palm oil.
N= normality of NaOH solution
V= volume of NaOH solution used in mL
W= weight of sample

For Palm Oil Sample 1 For Palm Oil Sample 2 For Palm Oil Sample 3
FFA% FFA% FFA%
25.6  0.1N  3.6mL 25.6  0.1N  3.6mL 25.6  0.1N  3.6mL
  
5.00 g 5.03 g 5.01g
 1.843%  1.832%  1.840%

Mean of FFA (%)

1.843%  1.832%  1.840%

3
 1.838%
The standard deviation (SD) is a measure of the amount of variation or dispersion of the values
obtained in the experiment.

Standard Deviation (SD)

(1.843  1.838) 2 %  (1.832  1.838) 2 %  (1.840  1.838) 2 %

3 1
 5.70  10 3%

The relative standard deviation (RSD) is the ratio of the standard deviation to the mean. It is used to
express the precision of the experiment.

Relative Standard Deviation (RSD)

5.70  10 3%
  100%
1.838%
 0.31%
Acid value = % FFA as palmitic acid × 2.19, where the value of 2.19 is the conversion factor for
palmitic acid.

Acid value for Palm Oil Acid value for Palm Oil Acid value for Palm Oil

Sample 1 Sample 2 Sample 3

 1.843%  2.19  1.832%  2.19  1.840%  2.19
 4.036%  4.012%  4.030%

Mean of acid value (%)

4.036%  4.012%  4.030%

3
 4.026%

Standard Deviation (SD)

(4.036  4.026) 2 %  (4.012  4.026) 2 %  (4.030  4.026) 2 %


3 1
 0.0125%

Relative Standard Deviation (RSD)

0.0125%
  100%
4.026%
 0.31%
Discussion：

Palm oil is triglycerides which composed of esterified of glycerol and specifically 16-carbon

saturated fatty acid. Its chemical formula is CH3(CH2)14COOH. In this experiment, the free fatty acid

content and acid value of palm oil are determined by using titration method. The free fatty acid

content is the amount of free fatty acid, (RCOO-) present in the palm oil. The acid value is defined as

the amount of milligrams of sodium hydroxide, NaOH used to neutralise the free acid in 1 gram of

palm oil. (Azeman, Yusof and Othman, 2015) During the experiment, the 5g of palm oil sample are

weighted and dissolved in neutralised 95% ethanol. The neutralised ethanol is used as solvent

because it can dissolve palm oil completely and neutralised ethanol would not undergo any chemical

reaction with the palm oil. During the titration, the phenolphthalein indicator is used because the

palm oil is weak acid while the sodium hydroxide is strong base, the pH at the equivalence point is

greater than 7 and the phenolphthalein turns from colourless to pink colour over a pH range of about

8.2 to 10.(Jeiyendira and Dave, 2013) In titration, the sodium hydroxide is react with palm oil, the

fatty acid, RCOOH in palm oil is neutralised to form fatty acid salt, RCOONa and water. (Gooch,

2011)The chemical reaction is called saponification and the reaction process is showed in Figure 1.1.

Figure 1.1: Saponification reaction of palmitic acid with sodium hydroxide.

From table 1, the volume of 0.1N sodium hydroxide, NaOH used to titrate three palm oil samples are

the same which is 3.6 mL. Based on the formula of FFA% calculation, the calculated mean free fatty

acid content, FFA% in palm oil is 1.838%. The calculated mean acid value is 4.026% which multiple

the FFA% with value of 2.19 where is the conversion factor for palmitic acid. (Salimon, 2016) The

RSD value of this experiment is very small, 0.31% and it can prove that the results obtained are

consistant and high accuracy. Based on the standards by Malaysian Palm Oil Board (MPOB), the

basic quality specifications of crude palm oil are maximum 5 % FFA and low acid value due to
high-quality crude palm oil. (Salimon, 2016) Therefore, the FFA% value of palm oil sample

analysed is in the acceptance range. If crude palm oil with high level of FFA%, it will show its lower

ability due to the enzymatic and microbial lipase reactions of palm fruit, as well as the storage of

crude palm oil under bad conditions such as high temperature and high moisture which can affect the

quality of oil. (Hashim, Yusup and Arlabosse, 2019) Therefore, heating process such as sterilization

process helps to inactivate the lipase enzyme in the fruits and prevent the increment of FFA content.

(Hashim, Yusup and Arlabosse, 2019) Sterilization process is also known as the most important

process in the palm mill to achieve low FFA content. (Hashim, Yusup and Arlabosse, 2019)

Conclusion：

In this experiment, the free fatty acid content, FFA% of palm oil sample is 1.838%. The acid value of

palm oil sample is 4.026%. The FFA% and acid value of this palm oil sample is consider

high-quality crude palm oil.

References:
Azeman, N. H., Yusof, N. A. and Othman, A. I. (2015) ‘Detection of free fatty acid in crude palm
oil’, Asian Journal of Chemistry. doi: 10.14233/ajchem.2015.17810.
Gooch, J. W. (2011) ‘Saponification’, in Encyclopedic Dictionary of Polymers. doi:
10.1007/978-1-4419-6247-8_10281.
Hashim, H., Yusup, S. and Arlabosse, P. (2019) ‘Extraction of crude palm oil (CPO) using thermally
assisted mechanical dewatering (TAMD) and their characterization during storage’, in 6TH
INTERNATIONAL CONFERENCE ON ENVIRONMENT (ICENV2018): Empowering Environment
and Sustainable Engineering Nexus Through Green Technology. doi: 10.1063/1.5117130.
Jeiyendira, D. and Dave, K. (2013) ‘A Novel, Inexpensive and Less Hazardous Acid-Base Indicator’,
Journal of Laboratory Chemical Education. doi: 10.5923/j.jlce.20130102.04.
Mettler Toledo. (n.d.). Blank Value for Free Fatty Acid Determination. [online] Available at:
https://www.mt.com/my/en/home/supportive_content/ana_chem_applications/titration/AP006.html
[Accessed 16 Nov. 2019].
Salimon, J. (2016) ‘FREE FATTY ACIDS SEPARATION FROM MALAYSIAN HIGH FREE
FATTY ACID CRUDE PALM OIL USING MOLECULAR DISTILLATION’, Malaysian Journal
of Analytical Science. doi: 10.17576/mjas-2016-2005-08.
Tech, R. (2019). Acid Number to FFA Conversions | Biodiesel Chemsitry. [online] Make Biodiesel.
Available at:
http://www.make-biodiesel.org/Biodiesel-Chemsitry/acid-number-to-ffa-conversions.html [Accessed
16 Nov. 2019].
Vitz, E., Moore, J., Shorb, J., Prat-Resina, X., Wendorff, T. and Hahn, A. (2019). Foods: Acid Value
and the Quality of Fats and Oils - Chemistry LibreTexts. [online] Chemistry LibreTexts. Available at:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Book%3A_ChemPRIME_(Moore_et_al.
)/14Ionic_Equilibria_in_Aqueous_Solutions/14.09%3A_Titration_Curves/Foods%3A_Acid_Value_
and_the_Quality_of_Fats_and_Oils [Accessed 16 Nov. 2019].