Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Review of different test methods for the evaluation of stability of biodiesel

Siddharth Jain *, M.P. Sharma
Biofuel Research Laboratory, Alternate Hydro Energy Centre, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand 247667, India

A R T I C L E I N F O A B S T R A C T

Article history: The vegetable oil, fats and their biodiesel suffer with the drawback of deterioration of its quality when it
Received 31 March 2010 is in contact with oxygen unlike petroleum diesel. There are various types of stabilities like oxidation,
Accepted 14 April 2010 storage and thermal, playing key roles in making the fuel unstable. The present paper is an attempt to
review all type of stability measuring test methods to find out the best method for stability
Keywords: measurement. From the review it is found that there are several methods to measure the stability of
Oxidation stability biodiesel but two test methods emerges the most likely choice for the purpose of measurement of
Thermal stability
oxidation stability of biodiesel. These are ASTM 2274 and 743 Rancimat test. A comparison between
Storage stability
these two shows that these may be used alternatively. Most commonly used methods to investigate the
Rancimat
Karl Fischer coulometer thermal stability are Rancimat test, ASTM D 6408-08, D 5304-06 and TGA/DTA. Rancimat test has been
Oil stability index (OSI) suggested as an important method to measure the thermal stability of oils, fats and biodiesel fuels.
ß 2010 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1938
2. Test methodology relating to fuel stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1938
2.1. Initial fatty oil composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1938
2.2. Primary oxidation products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1938
2.3. Secondary oxidation products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1939
2.4. Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1939
2.4.1. Iodine value (IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1939
2.4.2. Peroxide value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1939
2.4.3. Viscosity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1939
2.4.4. Structure indices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1939
2.4.5. Oxidizability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1940
3. Various stability test methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1940
3.1. Oxidation stability of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1940
3.1.1. Active oxygen method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1940
3.1.2. ASTM D2274, standard test method for oxidation stability of distillate fuel oil (accelerated method). Modified,
specifically for use with biodiesel by NREL, USA [50] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1940
3.1.3. ASTM D3241, standard test method for thermal oxidation stability of aviation turbine fuels (JFTOT procedure) [52] . . . . . . 1940
3.1.4. EN 14112, the Rancimat test, fat and oil derivatives. Fatty acid methyl ester (FAME). Determination of oxidation
stability (accelerated oxidation) test [53]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1940
3.1.5. ASTM D5483, standard test method for oxidation induction time of lubricating greases by pressure differential
scanning calorimetry [59] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1942
3.2. Storage stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1942
3.2.1. ASTM D 4625–04, standard test method for middle distillate fuel storage stability at 43 8C (110 8F) [63] . . . . . . . . . . . . 1942
3.2.2. Modified Rancimat test for storage stability [20,58] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1942
3.3. Thermal stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1942

* Corresponding author. Tel.: +91 9456382050; fax: +91 1332 273517.

E-mail address: [email protected] (S. Jain).

1364-0321/$ – see front matter ß 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.rser.2010.04.011
1938 S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947

3.3.1. ASTM D 6468-08, standard test method for high temperature stability of middle distillate fuels [65] . . . . . . . . . . . . . . . 1942
3.3.2. Rancimat test with a procedure specially modified for thermal stability evaluation [20] . . . . . . . .... . . . . . . . . . . . . . . . 1945
3.3.3. TGA/DTA method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . 1945
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . 1945
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . 1946
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . 1946

1. Introduction (IV) [4–6]. Two ASTM methods exist for measuring this parameter,
D1541 and D1959. The later determines total olefinic unsaturation
Numerous test procedures have been either developed or only in fuels that contain no conjugated polyunsaturation while
adopted to measure the various factors associated with oxidative the former accurately determines the total olefinic unsaturation
and thermal instability of biodiesels. Such test methods can be regardless of the isomeric configuration, but is a very tedious
categorized based on whether they measure initial fatty oil procedure involving a photographer’s darkroom for part of the
composition, primary oxidation products, secondary oxidation laborious sample work up. Accordingly, this procedure is seldom
products, physical properties, or carryout stability test. used in the fatty oils industry. Also, IV has been shown to be a poor
The compositional parameters pertaining to the initial fatty oil or predictor of relative oxidation stability of fatty oils and esters as
ester include the ester content, fatty acid chain distribution within well as the relative tendency of a biodiesel fuel to form engine
the fatty oil or ester and the type and extent of olefinic unsaturation. deposits [7]. More specifically, IV has been shown not to correlate
Special indices designed to consider the amount of allylic or bis- with OSI in a series of mixtures of pure methyl ester compounds
allylic carbons have been developed. Several methods directly [6].
measure the tocopherols or indirectly measure the impact of natural Several more useful indices have been developed using FAME
antioxidants have also been proposed. Primary oxidation products analysis results [6,7]. The allylic position equivalent (APE) is a
are hydroperoxides and conjugated dienes and procedures to theoretical measure of the number of singly allylic carbons present
measure both are established for fatty oils and esters. Secondary in the fatty oil or ester, assuming that all poly-olefinic unsaturation
oxidation products have been measured by many procedures is methylene-interrupted. The bis-allylic position equivalent
depending on the type of compounds of interest. Total acid number, (BAPE) is a similar theoretical measure of the number of doubly
anisidine value (aldehyde content) and an HPLC method for allylic carbons present in the fatty oil or ester. Both of these indices
polymers are among the most important. An index ‘TOTOX’ designed correlate with OSI IP [6]. The BAPE, in particular, has been shown to
to take into account both primary and secondary oxidation has also correlate with the OSI IP with an R2 value of 0.983. Of course, these
been proposed based on a weighted linear sum of peroxide value and two indices can be correctly calculated from FAME analysis only for
anisidine value. Physical properties that are sensitive to fatty oil fatty oils or esters derived from methylene-interrupted sources
oxidation include viscosity, refractive index and di-electric constant. such as rapeseed or soy. For oils that do not have methylene-
A number of accelerated stability test methods have been used interrupted poly-olefinic unsaturation (such as jojoba oil and
which involve the stressing of the fatty oil or ester by combination of meadowfoam oil), the standard APE and BAPE formulae are not
elevated temperature, time and enhanced oxygen exposure while valid. The APE and BAPE values of such oils must be calculated
measuring one or more oxidation-sensitive properties such as individually depending on the exact known isomeric structure of
peroxide value, insolubles, evolution of volatile short chain acids or the poly-olefinic unsaturation [7].
heat of reaction. Some of these methods include the Active Oxygen Over the last 25 years, several methods based on high
Method, ASTM D2274, ASTM D4625, oxidation stability index (OSI), performance liquid chromatography (HPLC) have been developed
or pressurized differential scanning calorimetry. The OSI test has to measure one or more of the four isomers of tocopherol [8–11].
gained acceptance in Europe where it is part of the biodiesel The HPLC method that has been used most recently in the biodiesel
specification. Within the U.S. it is a common research tool. The industry is ISO 993684 [3]. Several methods have been developed
Metrohm Rancimat apparatus is frequently used to measure OSI and to measure the ‘‘antioxidant power’’ of fatty oils and esters out of
the terms ‘‘Rancimat’’ and ‘‘OSI’’ are often used interchangeably in which one method uses an amperiometric procedure to determine
the literature while referring to the test method. However, no simple the oxidation potential of a fatty oil or ester [12]. The authors claim
stability test or single stability parameter appears to be adequate to that the most effective fatty oil antioxidants gave oxidation
define all the stability characteristics of biodiesel fuel. It is highly potentials between +0.4 V and +0.6 V relative to an Ag/AgCl
unlikely that any single new test will be able to completely define reference electrode. Two methods have been reported that use a
biodiesel stability either. stable colored radical that acts as a hydrogen scavenger for active
hydrogen available in antioxidants. As the radical captures the
2. Test methodology relating to fuel stability hydrogen, the color is reduced and the progress of this reaction can
be measured by appropriate measurements in the UV/Visible
2.1. Initial fatty oil composition spectra. One method uses a neutral radical 2,2-diphenyl-1-
picrylhydrazyl (DPPH) [13]. While another method uses a radical
The ester content of a biodiesel fuel, a basic property, should be cation 2,20 -azinobis (3-ethylbenzothiozoline-6-sulfonic acid)
known. An earlier method using gas–liquid chromatography (GLC) (ABTS) [14]. The main difference between the two methods is
has been used [1], but the standard method now used is usually a gas that the earlier method requires up to 6 h reaction time for the
chromatographic procedure (Pr EN 14103 or AOCS Ce 1-62) [2] color reduction reaction to come to equilibrium. While the later
commonly called FAME (fatty acid methyl ester) analysis [3]. This method has a reaction time of about 2.5 min.
procedure gives not only the percent ester in the fluid, but also the
percentage of the individual esters according to their fatty acid 2.2. Primary oxidation products
structure.
One of the oldest and most common methods of determining As already discussed, primary oxidation products are charac-
the level of unsaturation in a fatty oil or ester is the iodine value terized as conjugated diene hydroperoxides which can be
 S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947 1939

measured by ASTM D3703 or by similar procedures [15–20]. 2.4.3. Viscosity

Conjugated dienes are measured by UV adsorption at 232 nm as Viscosity has been found to increases with increase in chain
per ISO 365650 [20,21]. length (number of carbon atoms) and with increase in the degree of
saturation. FFAs are responsible for higher viscosity than the
2.3. Secondary oxidation products corresponding methyl or ethyl esters. Double bond configuration
influences the viscosity, i.e., cis double bond configuration results
A very sensitive wet method to detect carbonyl compounds and in lower viscosity than trans while the position of the double bond
a UV adsorption method used to determine unsaturated carbonyls affects the viscosity to less extent [41]. Since the oxidation
compounds have been reported [22]. The thiobarituric acid (TBA) processes lead to the formation of FFAs, isomerization of double
test was an old test to measure the levels of aldehydes produced bond, usually, cis to trans and formation of high MW products
during the oxidation of fatty oils [23]. However, the chemical increases the viscosity with increasing oxidation. Based on the
reaction critical to this procedure has more recently been shown to measurement of kinematic viscosities of four different biodiesel
produce significantly erroneous amounts of the final product fuels and their blends with diesel, Yuan et al. [42] have found a
measured during sample workup [24]. The anisidine value (AV) viscosity–temperature relationship similar to diesel. Further, a
test (EN ISO 6885 or AOCS Cd 18-90) [25] is a more reliable method relationship between viscosity and specific gravity was also
now used to determine aldehydes levels in oxidized fatty oils and developed that can estimate viscosity from specific gravity of
esters. A similar method using benzidine instead of anisidine has biodiesel. The accuracy of this method was found comparable to
been reported but was not used to any significant extent [26]. the weighted mass based semi log blending equation.
Several methods to measure volatile aldehydes in closed system
headspace have also been reported [27–29]. 2.4.4. Structure indices
Since oxidation is a multi-step reaction sequence involving both The allylic position equivalent (APE) is a theoretical measure of
primary and secondary species, an index has been proposed to the number of singly allylic carbons present in the fatty oil or ester
better track the oxidation process. This index, the TOTOX value, is assuming that all poly-olefinic unsaturation is methylene-inter-
defined as follows [30,31]:TOTOX ¼ 2  PV þ AVDevelopment of rupted. The bis-allylic position equivalent (BAPE) is a similar
acidic materials during oxidation is typically measured by simple theoretical measure of the number of doubly allylic carbons
titration such as Total Acid Number, ASTM D664 (TAN) present in the fatty oil or ester. Both APE and BAPE have been
[16,32,18,19,3]. Early methods to measure polymer levels in fatty correlated with oxidation stability index (OSI) and peroxide value
oils and esters have been proposed [33,34]. The procedure most [6].
often used in the biodiesel industry is BS EN ISO 16931, a size Knothe et al. [6] studied the influence of structure and
exclusion HPLC procedure using a refractive index detector [3]. A concentration of individual fatty compounds on the oxidation
similar procedure is AOCS Cd 22-91. stability of fatty acid esters. Other stability specifications like APE
and BAPE for allylic and bis-allylic position equivalents takes into
2.4. Physical properties account both the number and position of double bonds in the
chains. Knothe suggested APE and BAPE is better correlated to
The most obvious physical property used to measure oxidation vegetable oils in terms of observed properties [6].
is the viscosity because the polymerization will necessarily Knothe has suggested the following relation to determine the
enhance that property. Kinematic viscosity seems to be the most APE and BAPE values [12]:
often used procedure [16,18,19] although absolute viscosity could
APE ¼ 2x ðAC18:1 þ AC18:2 þ AC18:3 Þ (1)
also be used. Several studies have used refractive index to show the
formation of polymers [22,35–37]. The fatty oil or ester polymers
have higher refractive indices is undoubtedly the only reason why
a refractive index detector is used in the BS EN ISO 16931 BAPE ¼ AC18:2 þ 2  AC18:3 (2)
procedure. Di-electric constant has also been used as a means to
where A is the amount of each fatty compound.
measure the development of more polar oxidation products than
Jain and Sharma [43] have calculated APE and BAPE values for
the parent fatty oil or ester [34].
different oils ME using Eqs. (1) and (2) respectively and plotted the
The fuel stability can be studied with respect to the following
variation of induction period with APE and BAPE respectively
parameters.
which shows that as the APE and BAPE value decreases, the
induction period increases indicating the credibility of the
2.4.1. Iodine value (IV)
equations. But the value of R2 is 0.43 and 0.22 for APE and BAPE
It is one of the oldest and most common method to determine the
respectively which is very less and is not always true. The reason
magnitude of unsaturation in fatty oil or ester [6,4,5]. D1541 and
may be that the amount of natural antioxidants is different in
D1959 are the two available ASTM methods used to measure IV,
different oil MEs depends on the process of production and the
though it not necessarily a good method for assessing the stability as
process of distillation of biodiesel. The above results also indicate
it depends on the position of the double bonds available for
that the impact of APE is much on induction period than BAPE.
oxidation [7]. Knothe et al. have also showed that OSI of various
Knothe [12] has also developed a correlation between OSI &
FAME correlates better with respect to BAPE equivalents than IV [6].
BAPE as given below:
2.4.2. Peroxide value OSI ¼ 3:91  0:045  BAPE ðR2 ¼ 0:983Þ (3)
The peroxide value is less suitable for monitoring the oxidation
as it tends to increase and then decrease due to its further A plot of BAPE vs OSI calculated using Eq. (3) for different oil ME to
oxidation to form the secondary oxidation products [38,18,39]. check the credibility of the equation has also been plotted by Jain
When the peroxide value reached a plateau of about 350 mequiv./ and Sharma [43] which shows that the value of R2 is 1 indicating
kg ester during biodiesel (SME) oxidation, acid value and viscosity that the relation is applicable to all the MEs under consideration by
continue to increase monotonically [39]. Besides viscosity, the acid the authors.
value has a good potential as a parameter for monitoring biodiesel The relation between the OSI and induction period shows the
quality during storage [31,40]. value of R2 is very less (0.2172) which indicates that the relation is
1940 S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947

not applicable to all ME. The reason may be that the amount of 400 ml of iso-octane. The aged fuel/iso-octane mixture was also
natural antioxidants is different in different oil ME depends upon filtered through a separate pair of filters.
the process of production and the process of distillation of ASTM D2274 indicates that the test can discriminate between
biodiesel. Also same oil ME produced at different places may have very stable fuels and very unstable fuels. Unlike the Rancimat, this
different properties [43]. test does not provide any measure of induction period. It is
presumed that all antioxidant capacity in the neat biodiesel is
2.4.5. Oxidizability consumed during the test. Hence, this test is more a measure of the
Some authors have used another index of stability known as tendency of the B100 to form polymers and insolubles. For those
Oxidizability (OX) as given by [27]: concerned about the formation of these materials, D2274 is
probably a better screening tool [50].
0:02 ð%OÞ þ ð%LÞ þ 2 ð%LnÞ
OX ¼ (4) In general, each of the test methods showed the relative efficacy
100
of various antioxidants. The relative ranking was similar but not
where O refers to oleic acid (18:1), L refers to linoleic acid (18:2) always exactly the same. Test times and temperatures seem to
and Ln refers to linolenic acid (18:3). have a significant effect with some of the tests such as D2274.
The relation between Oxidizability (OX) and induction period
indicates that OX decreases with increase in induction period and 3.1.3. ASTM D3241, standard test method for thermal oxidation
since the value of R2 is very less (0.2255), the relationship stability of aviation turbine fuels (JFTOT procedure) [52]
therefore, is not very reliable parameter [43]. This test method measures the high temperature stability of gas
turbine fuels using the Jet Fuel Thermal Oxidation Tester (JFTOT)
3. Various stability test methods that subjects the test fuel to conditions that can be related to those
occurring in gas turbine engine fuel systems. The fuel is pumped at
Various procedures designed to accelerate the oxidative and/or a fixed volumetric flow rate through a heater after which it enters a
thermal instability of fatty oils have been developed or adopted precision stainless steel filter where fuel degradation products are
from similar procedures used in other industries (most notably the trapped. In this project, the precision filter had to be removed
fuels and lubricants industries). because it plugged too quickly. The apparatus uses 450 ml of test
fuel ideally during a 2.5 h test. The essential data derived are the
3.1. Oxidation stability of biodiesel amount of deposits on an aluminum heater tube as determined by
ellipsometry (an optical technique for measuring the thickness of
Different parameters and test methods to measure the thin films), and the rate of plugging of a 17 m nominal porosity
oxidation stability are given as below. precision filter located just downstream of the heater tube.
Because of the small sample size, the data are inconclusive and
3.1.1. Active oxygen method therefore further study to evaluate this test method is warranted.
The Active Oxygen Method, AOM (AOCS Method Cd 12-57) [44] The JFTOT could be a significant tool for studying high temperature
has been used for sixty years with different modifications [45–49]. deposit formation with B100. However, the JFTOT is not likely to be
This test procedure involves heating an oil sample at a useful as an oxidation stability test for specification purposes.
predetermined temperature while bubbling dry air through at a Multiple tests would be required to establish the induction period
set rate. The time (usually in hours) required for a specific peroxide of a given B100, the time and cost of which could be prohibitive.
value to be achieved is considered as the measured parameter. ASTM D3241 (JFTOT) will require additional study to determine
Sometimes, the rapid increase in PV is also used as the endpoint if it can be used to measure the oxidation stability of biodiesel. This
determination. test is quick and simple to perform. There are numerous methods
for quantifying the deposits formed although most are visual, so
3.1.2. ASTM D2274, standard test method for oxidation stability of not as useful. The ellipsometric tube-rating instrument shows
distillate fuel oil (accelerated method). Modified, specifically for use promise since the deposit color does not affect the measurement.
with biodiesel by NREL, USA [50] This test method is a specification test for aviation fuel so there is
A method similar to the active oxygen method has been already acceptance of the results for specification purposes. The
developed by the petroleum fuels industry as ASTM D2274 which greatest strength of this test may be as a measure of the tendency
uses a filtration and gravimetric determination to measure the of a biodiesel to form deposits on a hot metal surface. In general,
insolubles produced during a heated oxidation period in which O2 is there is currently insufficient data to recommend this test as a
bubbled through the sample (typically for 16 h at 95 8C) [51]. A specification test but it requires further additional study.
350 ml volume of filtered middle distillate fuel is aged at 95 8C for
16 h. Oxygen is bubbled through the sample at a rate of 3 l/h. After 3.1.4. EN 14112, the Rancimat test, fat and oil derivatives. Fatty acid
aging, the sample is cooled to approximately room temperature methyl ester (FAME). Determination of oxidation stability (accelerated
before filtering to obtain the filterable insolubles. Adherent oxidation) test [53]
insolubles are then removed from the oxidation cell and associated There are two new European standards for biodiesel: EN 14213,
glassware with trisolvent (a mixture of equal parts of toluene, for home heating fuel and EN 14214 for automotive diesel fuel.
acetone, and methanol). The trisolvent is evaporated to obtain the Both of these standards have stability requirements based on the
quantity of adherent insolubles. The sum of the filterable and Rancimat test as given below:
adherent insolubles expressed as milligrams per 100 ml, is reported
as total insolubles. As with the D4625 analyses, 100 ml of the aged,  Heating fuels: Fatty acid methyl esters (FAME)—stability require-
filtered fuel was mixed with 400 ml of iso-octane and filtered though ment: Rancimat Induction Period @ 110 8C  4 h.
Whatman GF/F filters (47 mm diameter) were used. After filtering  Automotive fuels: Fatty acid methyl esters (FAME) for diesel
the aged sample, but prior to solvent washing of the filters, an aliquot engines—stability requirement: Rancimat Induction Period @
of the filtrate was obtained for additional testing. The aliquot was 110 8C  6 h.
analyzed for total acid number (ASTM D664) and kinematic viscosity
at 40 8C (ASTM D445). As an additional analysis for biodiesel-soluble Because the Rancimat test is included in these two European
polymers, 100 ml of the aged and filtered fuel was mixed with specifications, it is in much wider use in Europe as compared to the
 S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947 1941

The OSI test is the commonly used test in Europe where

biodiesel fuels should meet the specification of an induction period
(IP) of at least 6 h when tested at 110 8C [54]. The Metrohm
Rancimat apparatus is frequently used to measure OSI and the
term ‘‘Rancimat’’ and ‘‘OSI’’ are often used interchangeably in the
literature while referring to the test method. OSI, commonly used
in experiments, requires to pass air through a heated sample of the
fatty oil or ester [55]. The air coming out of the sample is finally
passed through water contained in a tube fitted with a conductivity
meter (Fig. 2). A sharp rise in conductivity is interpreted as
indication of the formation of short chain water soluble carboxylic
acids, i.e., secondary oxidation products. Studies have indicated
that the primary acidic species formed in the Rancimat OSI test is
formic acid. The mechanism of decomposition of hydroperoxides
to form formic acid has been explained by Hasenhuettl et al. [56].
One significant difference regarding the use of the Rancimat test
in Europe vs the U.S. is that most of the B100 produced in Europe is
from rapeseed oil while most of the biodiesel produced in the U.S.
Fig. 1. Graphical determination of induction time (t) by the tangent method is made from soybeans or yellow grease. Because of its composition
(manual evaluation). (lower polyunsaturated content), the rapeseed methyl ester (RME)
tends to have significantly longer Rancimat induction periods than
United States and accordingly the quantum of data from running of either soy or yellow grease. Typical induction periods for RME are
the test on biodiesel samples is greater in Europe. 4–6 h as compared to 1–2 h for soy and yellow grease [57].
In Rancimat method, the oxidation is induced by passing a This test is well established in Europe and is included in several
stream of air at the rate of 10 l/h through biodiesel sample (3 g) European specifications. It is quick and simple to run and could be
kept at constant temperature (100, 110 and 120 8C). The vapors completed in a single work shift. It provides a repeatable measure
released during the oxidation process together with the air are of the antioxidant capacity of the biodiesel although the
passed into the flask containing 60 ml of demineralized water and relationship of that measure to the field has not been established.
fitted with an electrode for measuring the conductivity. The Several authors have reported the work done on oxidation
electrode is connected to a measuring and recording device. It stability using Rancimat test. BIOSTAB [58] project has reported a
indicates the end of IP when the conductivity begins to increase comparison between ASTM 2274 and Rancimat test as shown in
rapidly. This accelerated increase is caused by the dissociation of Fig. 3.
volatile carboxylic acids produced during the oxidation process This indicates the relationship between the filterable, adherent
and absorbed in the water. When the conductivity of this solution and total insoluble with induction period. Fig. 3 indicates that the
is recorded continuously, an oxidation curve is obtained whose total insolubles and filterable insolubles are in batter agreement
point of inflection, known as the IP, can be calculated by the point with Rancimat induction period. This, in turn, indicates that both
of intersection of two tangents as shown in Fig. 1. the tests can be used interchangeably.

Fig. 2. Schematic of Rancimat test [55,56].

1942 S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947

method make it a poor choice as a convenient and predictive

measure of oxidation stability.
ASTM D4625 is an excellent method for estimating the long-
term storage stability of middle distillate petroleum fuels. One
week of storage at 43 8C is widely accepted as equivalent to 4
weeks at 15 8C (underground, ambient storage). While the same
relationship has yet to be proven for B100, most researchers have
tended to accept that the correlation holds. This makes D4625 an
excellent research method but it is not acceptable as a specification
test.

3.2.2. Modified Rancimat test for storage stability [20,58]

Rancimat test may also be used for testing the storage stability
of biodiesel. For the purpose of checking the storage stability, it is
Fig. 3. Comparison between ASTM 2274 and Rancimat induction period modified by BIOSTAB project [20,58]. A stream of purified air (10 l/
h) is passed above the surface of 3 g of sample heated at 80 8C
during 24 h and peroxide value, ester contents and polymer
3.1.5. ASTM D5483, standard test method for oxidation induction time content are measured. The modified Rancimat test is suitable for
of lubricating greases by pressure differential scanning calorimetry use in terms of repeatability, significance and is easier to handle.
[59]
ASTM D5483 is failed to give useful results regarding the 3.3. Thermal stability
relative stabilities of various fuels. Pressurized differential
scanning calorimetry (PDSC) has been used in several studies to 3.3.1. ASTM D 6468-08, standard test method for high temperature
measure the oxidation stability of fatty oils and esters with and stability of middle distillate fuels [65]
without added antioxidants [60–62]. When run using an isother- Two 50-ml volumes of filtered middle distillate fuel were aged
mal procedure, the time required to detect an exothermic reaction for 90 or 180 min at 150 8C in open tubes with air exposure. After
is considered the induction time. When run using a non-isothermal aging and cooling, the fuel samples were filtered and the average
procedure, the temperature, where an exothermic peak is detected, amount of filterable insolubles is estimated by measuring the light
is called the oxidation temperature (OT). reflectance of the filter pads. An unused filter pad and a commercial
black standard define the 100 and 0% extremes of the reflectance
3.2. Storage stability rating range respectively.
The reflectance measurement works well with petroleum diesel
3.2.1. ASTM D 4625–04, standard test method for middle distillate fuel fuel because the particles formed during the aging are typically
storage stability at 43 8C (110 8F) [63] brown or black. Hence, increased amounts of particles result in
Standard Test Method ASTM D4625 is the most widely accepted decreased reflectance. With biodiesel, the particles and polymers
test method for assessing the storage stability of middle distillate formed have almost no visible color. Therefore, the increased
petroleum fuels. The fuel is stored at 43 8C for selected periods up amounts of biodiesel particles/polymers result in little or no
to 24 weeks. One week of storage in this test is generally accepted change in reflectance. This means that the test gives the best
as equivalent to 1 month of storage at 17 8C (65 8F). Typically, a results when the biodiesel particles/polymers are measured
sample is filtered to determine total insolubles on a weekly basis. gravimetrically.
For testing of biodiesel, Whatman GF/F filters (47 mm diameter) ASTM D6468 supports the widely held assertion that the
were used. After filtering the aged sample, the filtrate was analyzed thermal stability of B100, as measured by this test, is very good. In
for total acid number (ASTM D664) and kinematic viscosity at 40 8C the BIOSTAB project, both B100 and petroleum diesel samples
(ASTM D445). were tested. The B100 samples had very little thermal degradation
As an additional analysis, 100 ml of the aged, filtered fuel was as measured either by reflectance or filter weight. However, the
mixed with 400 ml of iso-octane to precipitate any polar polymeric petroleum diesel samples showed significant differences in their
materials that may have formed as a result of ageing. The aged fuel/ thermal stability characteristics.
iso-octane mixture was filtered through a separate pair of filters.
This was done in a previous study that concluded that ageing of
B100 under these conditions does not result in the formation of
insolubles because the oxidized and polar polymers formed are
soluble in the biodiesel. Dilution with a non-polar solvent such as
iso-octane, was shown to result in precipitation of these polymers.
This method indicates that viscosity is not sufficiently sensitive
to changes in polymer formation. Also, the conditions of this test
are very mild compared to some of the other test methods often
used to measure oxidation stability. This test is more representa-
tive of changes in the biodiesel during longer periods of quiescent
storage, typically, at temperatures below 30 8C. It is not
representative of the higher temperatures and greater oxygen
exposure in a diesel vehicle fuel system.
Although, it is generally an accepted test for the storage stability
of petroleum fuels, similar correlations to the storage of biodiesel
have yet to be developed. Until those correlations have been
developed, the ability of the test to measure storage stability is
unclear. The milder conditions and very long test times used in this Fig. 4. TGA thermogram showing various parameters [66].
Table 1
Comparison of different test methods for stability of biodiesel.

S.N. Type of stability Name of test Stability parameter (s) Merits Demerits Remark References
method

1. Oxidation (i) Active oxygen Induction period – (a) Costly Not good [44–49]
method
(b) Labor intensive

(ii) ASTM D2274 Total insolubles, (a) The test can discriminate (a) Unlike the Rancimat, this test gives Good [50,51,57]
filterable insolubles between very stable no measure of induction period
and adherent insolubles and very unstable fuels
(b) Test time and temperatures seem to
have a significant effect on the results
and chances of error are high
(c) No specification is available in any

S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947
national or international standards

(iii) ASTM D3241 (a) The JFTOT could be a (a) Because of the small sample size, Not good [52,57]
significant tool for the data are inconclusive
studying high temperature
deposit formation with B100
(b) This test is quick and (b) The JFTOT is not likely to be
simple to perform useful as an oxidation stability
test for specification purposes
(c) Multiple tests would be required
to establish the induction period
of a given B100
(d) The time and cost could
be prohibitive
(e) Requires additional study
to determine if it can be used
to measure the oxidation
stability of biodiesel
(f) No specification is available
in any national or international
standards

(iv) EN 14112 Induction period (a) Simple – Very good [53–58]

(b) Less chances of error
(c) Repeatability is good
(d) Specifications are
available in ASTM and
European standards
related to induction period

(v) ASTM D5483 – (a) Do not give useful results regarding Not good [57,59–62]
the relative stabilities of various fuels
(b) No specification is available in any
national or international standards

2. Storage (i) ASTM D 4625–04 Total insolubles, (a) The conditions of this (a) This method indicates that Good [57,63]
filterable insolubles test are very mild viscosity is not sufficiently
and adherent insolubles compared to some of sensitive to changes in
the other test methods, polymer formation
often, used to measure
oxidation stability

1943
 1944
Table 1 (Continued )

S.N. Type of stability Name of test Stability parameter (s) Merits Demerits Remark References
method

(b) This test is more (b) It is not representative

representative of changes in of the higher temperatures
the biodiesel during longer and greater oxygen exposure
periods of quiescent found in a diesel vehicle
storage, typically at fuel system
temperatures below 30 8C
(c) It is an excellent method (c) Need of very long test
for estimating the long-term times used in this
storage stability of middle method make the
distillate petroleum fuels method a poor choice
as a convenient and
predictive measure

S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947
of oxidation stability
(d) No specification is
available in any
national or international
standards

(ii) ASTM D 5304–06 Total insolubles, – (a) No specification is Not good [64]
filterable insolubles available in any national
and adherent insolubles or international standards

(iii) Modified Induction period (a) Less time consuming Very good [20,58]
Rancimat
test for storage
stability
(b) Good repeatability
(c) Chances of error are very less

3. Thermal (i) ASTM D 6468–08 Total insolubles, (a) It is very short 90-minute (a) There is no active addition of Good [57,65]
filterable insolubles test which makes it very air or oxygen to the fuel during
and adherent insolubles attractive test for quality testing this test is therefore not
assurance and quality control useful for measuring oxidation stability
(b) This test method does not provide
a useful discrimination between biodiesel
fuels of varying quality
(c) No specification is available in any
national or international standards

(ii) Modified Rancimat Polymers (a) Less time consuming (a) No specification is available in any Very good [20,58]
national or international standards
(b) Modified form of
ASTM D6468-08
(c) Less error
(d) Good repeatability

(iii) TGA/DTA Activation energy, (a) Less time consuming (a) Relatively costlier Very good [66–81]
onset temp, oxidation
induction time and
specific heat
(b) High precision
(c) Good repeatability
 S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947 1945

ASTM D6468 has existed in nearly the same form (albeit different In most cases, TGA analysis is performed in an oxidative
names) for over 60 years. Its very short 90-min test time makes it a atmosphere (air or oxygen and inert gas mixtures) with a linear
very attractive test for quality assurance and quality control. The temperature ramp. The maximum temperature is selected so that
150 8C test temperature makes this test quite severe. There is no the sample weight is stable at the end of the experiment, implying
active addition of air or oxygen to the fuel during testing so this test is that all chemical reactions have been completed.
not as useful for measuring oxidation stability. Also, this test method The onset temperatures (Ton) as shown in Fig. 4 can be used to
has historically relied on estimating the amount of insolubles indicate the resistance of the oil to thermal degradation deter-
formed based on the darkness of the material trapped on a filter pad. mined by extrapolating the horizontal baseline at 1% degradation.
Biodiesel insolubles tend to be far less dark in color than petroleum The intercept of this line with the tangent to the downward portion
diesel and as such, are more difficult to quantify using optical of the weight curve was defined as the onset temperature. As the
methods. Gravimetric measurement of insolubles provides more oil is oxidized, its onset temperature decreases [66].
reliable quantification. Biodiesel tends to be very thermally stable Table 1 is representing the comparison of different test methods
but less oxidatively stable when compared to petroleum diesel. This available for different type of stabilities.
test method does not provide a useful discrimination between The above table summarizes the methods of various stabilities
biodiesel fuels of varying quality. This test may, however, be useful carried out by various researchers. The oxidation, thermal and
for B20 but more work is still required to be done. storage stability of biodiesel has been determined by using various
methods which includes Active oxygen method, ASTM D2274,
3.3.2. Rancimat test with a procedure specially modified for thermal ASTM D3241, EN 14112, ASTM D5483, ASTM D4625-04, ASTM
stability evaluation [20] D5304-06, ASTM D 6468-08, Modified Rancimat, TGA/DTA based
The Rancimat apparatus has also been adopted to measure on various stability parameters such as PV, AV, viscosity,
thermal stability by not using an airflow and measurement of tocopherols contents, OSI, total insolubles, filterable insolubles,
polymer content in an 8 g sample after 6 h at 200 8C [20,58]. A more adherent insolubles, linoleic acid contents, insolubles, onset
traditional test for thermal stability, ASTM D6468, requires heating temperature, enthalpy of crystallization, oxidation induction time,
the sample at 150 8C for either 90 or 180 min. The sample is then etc.
cooled and either filtered to determine filterables via a total From the above table, it is concluded that the most useful and
reflectance meter or gravimetrically in a manner similar to ASTM beneficial method for oxidation stability is EN 14112 method,
D227490. The modified Rancimat test is suitable for use in terms of which is not only less time consuming but also chances of error is
repeatability and it is easy to handle [58]. very less with good repeatability. Also the method is compared
with ASTM D2274 which is a standard test method to measure the
3.3.3. TGA/DTA method oxidation stability. Modified Rancimat test for storage stability is
Thermal stability of oils depends on their chemical structures. found to be a useful method for storage stability with less time
Oils with a high proportion of unsaturated fatty acids are less consuming, less error and good repeatability. Specifications are
stable than the saturated ones [66]. In the recent years, thermal also available in international as well as national standards for
analysis was successfully used to study the physical properties, Rancimat test. For thermal stability TGA/DTA and modified
chemical reaction and the thermal stability of oils. Thermo Rancimat test are found to be more appropriate. However, no
analytical methods, especially, thermogravimetry analysis (TGA) specification is available in national and international standard for
has the advantages of being precise, sensitive and fast needing thermal stability.
small amount of sample [66]. The most effective test parameter is the induction period for
Thermo analytical methods include a group of techniques in oxidation stability, viscosity, linoleic acid contents, AV, onset temp
which the thermal behavior or thermal properties of a material are and order of reaction for thermal stability and viscosity, induction
determined as a function of temperature. The thermal tests period for storage stability. But no perfect correlation has been
measure the change of weight and enthalpy as the sample is found between these stability parameters. Therefore, there is a
heated. TGA has been extensively used in polymer science for need to develop co-relations between various stability parameters
measurement of degradation of polymer [67–69]. The equipment of vegetable oil and to study the effect of Rancimat induction
continuously monitors the loss of sample weight while the sample period on various stability parameters e.g. insoluble formation,
is heated in isothermal or dynamic conditions. Thermal analysis viscosity, linoleic acid contents, onset temperature, order of
techniques have been used for the characterization of edible oils reaction, etc. The results of such studies would prove to be
and fats by studying several properties such as thermo-oxidative valuable to develop correlations between the various stabilities of
behavior and stability [70–72], specific heat [73], thermal oils and their biodiesels and effect of various parameters on the
decomposition activation energy [74], temperature and enthalpy oxidation, thermal as well as storage behavior.
of crystallization [75–78], effect of antioxidants on thermal
stability of oils [74,79], degree of unsaturation from melting and 4. Conclusion
crystallization oil profile curves [80] and high-pressure oxidation
induction period measurements [81]. From the various experiments, it is concluded that two test
Thermogravimetric analysis is normally carried out either in methods emerges the most likely choice for the purpose of
the presence of air or in an inert atmosphere, e.g., N2, He, Ar and the measurement of oxidation stability of biodiesel. These are ASTM
weight loss is recorded as a function of increasing temperature. The 2274 and 743 Rancimat test. A comparison between these two
measurements are, sometimes, performed in O2 atmosphere (1–5% shows that these may be used alternatively. The test methods were
O2 in N2 or He) and sometimes in a lean oxygen atmosphere (1–5% evaluated for their ease of use, applicability to the measurement of
O2 in N2 or He) to slow down the oxidation process. Some biodiesel, ability to discern additive effects and ability to
instruments also record the temperature difference between the discriminate between biodiesel samples of various levels of
sample and one or more reference pans (differential thermal oxidation stability. Most commonly used methods to investigate
analysis or DTA) or the heat flow into the sample pan compared to the thermal stability are Rancimat test, ASTM D 6408-08, D 5304-
that of the reference pan (differential scanning calorimetry, or 06 and TGA/DTA. Rancimat test has been suggested as an
DSC). The later can be used to monitor the energy released or important method to measure the thermal stability of oils, fats
absorbed via chemical reactions during the heating process. and biodiesel fuels. Further, the modified Karl Fischer (KF)
1946 S. Jain, M.P. Sharma / Renewable and Sustainable Energy Reviews 14 (2010) 1937–1947

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