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inform October 2003 Volume 14 (10) ANALYTICAL ARTICLE 651

Peroxide value determination

Hans-Jochen Fiebig

Over a period of many years, various to the flask. After exactly one minute from tors such as sample size, reaction tem-
methods have been developed for the the time of the addition of the potassium perature, and reaction time as well as sec-
determination of peroxides in fats and iodine, 100 cc. of water are added and ondary reactions influenced the results
oils. The general principle of most of the the liberated iodine is titrated with 0.1 of the determination. However, the first
methods is the liberation of iodine from N or 0.01 N sodium thiosulfate, depend- three factors should normally have no
potassium iodide in an acid medium. The ing on the amount of iodine liberated. effect when the methods are standard-
method according to D.H. Wheeler was This method was examined by sev- ized. But these factors are often respon-
standardized more than 50 years ago by eral other workers, who found that sam- sible for the differences when the results
different standardization bodies and is ple size strongly influenced the PV obtained by different methods are com-
widely used by producers, receivers, and obtained, producing a reduction of 3050% pared.
official laboratories to control commodities. in PV when the sample size was increased. According to Sehers investigations,
In national and international food Decreasing the sample size increased the the sample size is not the critical factor,
legislation (including the Codex PV by up to 140150%. provided there are no problems with
Alimentarius), limit values for peroxide To achieve a more reliable method, the solubility of the oil or fat. Depending
values (PV) are often fixed. Owing to R.F. Paschke and D.H. Wheeler modified on the quantity of the test portion, he
anomalies in the reproducibility of the the original Wheeler method in 1944 (Oil determined a PV of 9.3 meq O 2 /kg for
results, slight differences between the and Soap 21:5257, 1944). Sample weight 0.6 g of linseed oil, and 4.8 meq O 2 /kg
standardized methods have been noted. was reduced to one gram, reaction time with a test portion of 2.7 g of the same
Interestingly, the cause of these problems increased from one minute to one hour, oil. According to his investigations, the
had already been reported in the litera- and CO 2 was used to minimize further difference was based only on the solu-
ture of the 1940s and 1950s. oxidation during the analyses. bility of the oil. Furthermore, he found a
C.H. Lea in 1931 published a method In 1946, Lea revised his earlier reaction time of 5 minutes was necessary
for the determination of peroxides in fats method, simplified many details, and rather than the 3 to 4 minutes proposed
and oils. He heated 1 g of fat with 12 g adopted the same solvent and one-hour earlier by other workers.
of powdered potassium iodide in a mix- reaction time from the Paschke and The method for the determination of
ture of chloroformacetic acid and then Wheeler method. He suggested that the PV according to Wheeler was adopted
titrated the liberated iodine with 0.002 N increase in PV observed in earlier pro- early on by several international organ-
sodium thiosulfate solution. The method cedures, when the quantity of fat taken izations including the Association of
gave reproducible results at a given sam- for the determination was reduced, was Analytical Communities (AOAC
ple weight but was inconvenient and even due to an increasing error resulting from International), AOCS, the International
somewhat hazardous to use since the sol- further oxidation of the fat by dissolved Union of Pure and Applied Chemistry
vent mixture was heated to its boiling oxygen. He introduced new procedures (IUPAC), and national bodies such as the
point. A year later, D.H. Wheeler pub- for a cold method as well as a hot method French standardization system
lished a greatly simplified, rapid, and in which oxygen exclusion was adequate. Association franaise de normalisation
more convenient method for the deter- Today, the hot method is known as the (AFNOR), British Standards Institute
mination of peroxides or active oxygen method according to Sully and is still (BSI), and DGF. Whereas the original
in vegetable oil. He suggested that the used for the determination of the PV in method used a mixture of acetic acidchlo-
sample size and the normality of the thio- fatty acids that are difficult to dissolve roform, newer versions have replaced this
sulfate solution should be varied if the (e.g., German Standard Methods for the solvent by an acetic acidisooctane mix-
levels of peroxides differed greatly. The Analysis of Fats and Other Lipids, edited ture for safety reasons. Unfortunately, all
following working protocol is taken from by the German Society for Fat Science these standardized methods differ slightly,
his publication in Oil and Soap (9:8997, [DGF], Wissenschaftliche Verlagsge- above all in the sample size that is required
1932): sellschaft GmbH, Stuttgart, 2002). But to perform the method. On the other hand,
Three to ten grams of oil are dis- Leas modified method gave generally it is interesting to see that all standard-
solved in 50 cc. of solvent mixture (60 lower results than the other methods. ized methods stick to the reaction time
per cent glacial acetic acid, 40 per cent In 1958 A. Seher published a survey of 1 minute, despite other recommen-
chloroform) and 1 cc. of saturated potas- on the determination of PV (Fette Seifen dations.
sium iodine solution [is] added. The mix- Anstrichmittel 60:264267, 1958). From Today, there are numerous analyti-
ture is stirred by giving a rotary motion many tests, he concluded that several fac- cal procedures for the measurement of
652 ANALYTICAL ARTICLE inform October 2003 Volume 14 (10)

PV. In all cases the results and the accu- tion prescribed for the determination.
racy of the methods depend on the exper- Table 1 The following unpublished table
imental conditions, as the method is highly Mass of test portion according to (Table 2) from the Institute for Lipid
empirical. Below, the most commonly ISO 3960:1977 Research of the Federal Center for Cereal,
used methods are discussed, together with Expected Mass of Potato and Lipid Research in Mnster
the principle on which they are based. peroxide value test portion (g) (Germany) shows this influence of the
AOCS has standardized a method for sample size on PV.
PV determination with chloroform (Cd 0 to 12 5.0 to 2.0 It can be seen that PV increases with
8-53) and with isooctane (Cd 8b-90). The 12 to 20 2.0 to 1.2 decreasing sample size. In further work,
latter method uses a mixture of acetic 20 to 30 1.2 to 0.8 the reaction time was doubled from 1 to
acidisooctane and a sample size of 5 30 to 50 0.8 to 0.5 2 minutes. In this case, the result for
g. The reaction time is 1 minute, and the 50 to 90 0.5 to 0.3 the determination of the PV with 5 g is
reaction mixture is titrated either with a 67 instead of 41. These results are in good
0.1 N sodium thiosulfate solution (for PV ing on the expected PV (see Table 1). For agreement with the literature-quoted val-
10150) or with 0.01 N sodium thiosul- the titration, 0.01 N sodium thiosulfate ues. Therefore, determination of the PV
fate if the titration is less than 0.5 mL. is used. The reaction time is 1 minute. is mainly dependent on the sample size
For a full validation, AOCS prescribes A national German standard method and the reaction time. Fortunately, the
the use of 0.001 N sodium thiosulfate (DGF C-VI 6a), published in 1984, pre- reaction time has been standardized within
solution. In the scope, it is stated that the scribes a sample size of 1 g for PV >2 and international methods to 1 minute, even
method is applicable to all normal fats 5 g for PV 2. After a reaction time of 1 if lower PV are obtained.
and oils, including margarine, but that it minute, the liberated iodine is titrated PV is a commonly used parameter.
is highly empirical, and any variation in with 0.1 N sodium thiosulfate or with The problem of different quantities of
the test procedure may produce erratic 0.01 N sodium thiosulfate if less than 0.5 sampleprobably also the reason for bad
results. mL is used. reproducibility limits in ring testsneeds
The International Organization for The determination of PV according to be addressed by the different stan-
Standardization (ISO) in 1977 published to the Olive Oil Regulation (EEC: dardization bodies and must be harmo-
the first edition of ISO 3960: Animal and European Economic Community, fore- nized soon. This is the only way to avoid
Vegetable Fats and OilsDetermination runner of the European Union) No. 2568/91 problems, and long debate, on the results
of Peroxide Value. This version used an is identical to IUPAC 2.501 and still uses obtained by different methods for the
acetic acidchloroform mixture and a the acetic acidchloroform mixture as determination of PV. ISO/TC 34/SC 11,
sample size dependent upon the expected solvent. The International Olive Oil the subcommittee of ISO TC 34 respon-
PV, as shown in Table 1. Council (IOOC) Trade Standard Applying sible for ISO 3960, is prepared to take
The reaction time is 1 minute. This to Olive Oil and Olive-Pomace Oil pre- the lead in a global harmonization process.
table for different sample weights is also scribes the methods ISO 3960 and IUPAC
used in IUPAC method 2.501. Titration
is performed with 0.01 N and 0.002 N
2.501 for PV, whereas the Draft Revised
Codex Standard for Olive Oils and Olive
Background resources
sodium thiosulfate for PV from 012 and Pomace Oils (Report of the 18th Session AOAC International Methods, Gaitherburg,
1290, respectively. of the Codex Committee on Fats and Oils, Maryland.
In 1998, ISO published the second London, 2003) quotes ISO 3960:2001 AOCS, Official Methods and Recom-
edition of ISO 3960 using acetic and AOCS Cd 8b-90. mended Practices of the American Oil
acidisooctane, and the third edition was As can be seen from this discussion, Chemists Society, 5th edn., AOCS Press,
published in 2001. ISO 3960:2001 still the main difference in these standardized Champaign, Illinois, 1997.
prescribes different sample sizes depend- methods is the quantity of the test por- International Organization for
Standardization, Geneva, Switzerland.
International Union of Pure and Applied
Table 2 Chemistry, Research Triangle Park,
Dependence of peroxide value on sample size North Carolina.
German Standard Methods for the Analy-
Sample size 5g 3g 2g 1.2 g 1g 0.8 g 0.6 g 0.4 g Dev.b sis of Fats and Other Lipids,
Peroxide valuea 3 5 158% Wissenschaftliche Verlagsgesellschaft,
5 7 150 Stuttgart, Germany.
5 8 149
8 9 10 10 123 Hans-Jochen Fiebig is chairman of
9 14 149 ISO/TC34/SC11: Animal and Vegetable
16 16 19 20 123 Fats and Oils. He may be contacted at
27 31 33 33 122 the Institute for Lipid Research, Federal
41 77 83 92 222 Center for Cereal, Potato and Lipid
a Titration with 0.01 N Na S O .
Research, Piusallee 68-76, 48147
2 2 3 Mnster, Germany; e-mail: hjfiebig@uni
bDeviation related to a sample size of 5 g.