Iodine value

The iodine value (IV) has been included in the European biodiesel stan­dards to purportedly address the issue of oxidative stability and the propensity of the oil or fat to polymerize and form engine deposits. The IV is a measure of the total unsaturation of a fatty material measured in grams of iodine per 100 g of sample when formally adding iodine to the double bonds. An IV of 120 has been specified in EN 14214 and 130 in EN 14213, which would largely exclude vegetable oils such as soybean and sunflower oils as biodiesel feedstock. Thus the IV has not been included in biodiesel standards in the United States and Australia, and is limited to 140 in the South African standard (which would permit sun­flower and soybean oils); the provisional Brazilian standard requires that it only be noted.

The IV of a vegetable oil or animal fat is almost identical to that of the corresponding methyl esters; however, the IV of alkyl esters decreases with higher alcohols used in their production since the IV is molecular weight dependent. For example, the IV of methyl, ethyl, propyl, and butyl linoleate is 172.4, 164.5, 157.4, and 150.8, respectively [64].

The use of the IV of a mixture for such purposes does not take into consideration that an infinite number of fatty acid profiles can yield the same IV and that different fatty acid structures can give the same IV, although the propensity for oxidation can differ significantly [64]. Other, new structure indices termed allylic and bis-allylic position equivalents (APE and BAPE), which are based on the number of such positions in a fatty acid chain and are independent of molecular weight, are likely more suitable than the IV [64]. The BAPE index distinguishes mixtures having nearly identical IV correctly by their OSI times. Note that the BAPE index is the decisive index compared to the APE because it relates to the more reactive bis-allylic positions. Engine performance tests with a mixture of vegetable oils of different IVs did not yield results that would have justified a low IV [65, 66]. No relationship between the IV and oxidative stability has been observed in another investigation on biodiesel with a wide range of IV [52].