Energy 45 (2012) 798e805

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Energy
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Higher heating value (HHV) of vegetable oils, fats and biodiesels evaluation based
on their pure fatty acids’ HHV
Wanignon Ferdinand Fassinou*
Laboratoire d’énergie solaire e UFR-S.S.M.T., Université de Cocody (Côte d’Ivoire), 22BP582 Abidjan 22, Cote d’Ivoire

a r t i c l e i n f o a b s t r a c t

Article history: Higher heating value (HHV) is an important property of a fuel, especially for vegetable oils, fats and their
Received 24 August 2011 derivatives which are intended to replace petroleum fuels. There are lots of methods to evaluate the HHV
Received in revised form of a fuel. In this paper, the HHV of vegetable oils, fats and their derivatives (biodiesels) is calculated by
26 April 2012
using the HHV of their pure fatty acids/methyl esters. The study reveals that, to be in a good agreement
Accepted 4 July 2012
with the experimental values, the HHV of the neat compounds must be determined with the highest
Available online 28 July 2012
accuracy. With an error inferior to 2% by comparison to the experimental values, this work shows that
the HHV of pure fatty acids or that of methyl esters can be judiciously used to calculate the HHV of the
Keywords:
Higher heating value
biofuels which they are the components.
Biodiesel Ó 2012 Elsevier Ltd. All rights reserved.
Vegetable oil
Fat
Fatty acid composition
Pure fatty acid

1. Introduction
Fossil fuels prices fluctuation leads to search other energies to
replace them. Therefore, the research of new sources of energy is
becoming a priority for the development of human activities. In
that way, vegetable oils, animal fats and their derivatives (referred
to biodiesels) are intensively investigated to replace mineral oils.
One of the most important characteristics of a fuel is its higher
heating value (HHV) which is the amount of heat released during the
combustion of one gram of fuel to produce CO2 and H2O at its initial
temperature and pressure. It characterises the energy content of the
fuel. This property is also important for vegetable oils, animal fats
and their derivatives studied as potential fuels. Experimentally, an
oxygen bomb calorimeter is used to determine the HHV (e.g. ASTM
D240); however, many workers have investigated lots of indirect
methods to obtain this value. Their aim is to avoid the constraints of
experimental evaluations (time consumer, several laboratory equi-
pments.) or to find some relations between HHV and some prop-
erties of the fuel (molecular weight, cetane number, density,
viscosity, flash point.). Hence, Goering et al. [1] have measured
some physical properties and the heating value of eleven vegetable
oils. By using a Parr adiabatic calorimeter, Freedman et al. [2] and
Krisnangkura [3] have measured and calculated the HHV of fatty
* Tel.: þ225 07 21 33 66; fax: þ225 22 48 38 07.
E-mail addresses: faswaniferd@caramail.com, faswaniferd@yahoo.fr.
esters and triglycerides. Dutt et al. [4], Demirbas [5e7] and other
investigators have also estimated vegetable oils’ HHV experimen-
tally and by calculations. Thus, it has been shown that vegetable oils’
HHV can be calculated by using their saponification and iodine data
[3,5] or the carbon number and the number of double bonds [1].
Demirbas has shown that vegetable oils and their methyl esters
(biodiesels) HHV can be estimated by using their viscosity, density or
flash point [6]. He has determined also the HHV of vegetable oils,
alcohols and alkanes experimentally and by calculation from their
density and viscosity measurements [7]. Fassinou et al. [8] have
shown that the fatty acid composition of vegetable oils and bio-
diesels can be used to predict their HHV. They have also selected
some relations which can be used to calculate the HHV of these
biofuels by using the data of their ultimate analysis [9].
In the literature there is not enough data on the HHV of the pure
fatty acids or their derivatives although they are the main compo-
nents of vegetable oils, fats and biodiesels. However, the works of
Sadrameli et al., Freedman et al. can be cited. Sadrameli et al. have
measured the HHV of pure fatty acids and found, for saturated fatty
acids, a linear relation between HHV and density, carbon number,
molecular weight, respectively [10]. Freedman et al. have measured
the HHV of fatty esters (methyl and ethyl) and triglycerides; they
have established some linear equations for the prediction of their
HHV with their carbon number, their electron number and their
molecular weight, respectively [2]. Knothe has reported the HHV of
some pure fatty acids in Ref. [11].

0360-5442/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.energy.2012.07.011
 W.F. Fassinou / Energy 45 (2012) 798e805 799

Table 1 Although, there are numerous formulae to calculate the HHV of

Higher heating value (MJ/kg) of pure fatty acid/pure fatty esters collected from the vegetable oils, fats or their derivatives, a method which uses the
literature.
HHV of neat fatty acids is not widespread, at least to the author’s
Fatty acid Chemical Sadrameli Freedman Knothe knowledge. Therefore, the objective of this paper is to estimate the
(carbon chain: formula et al. (pure and Bagby (pure fatty HHV of vegetable oils, fats and biodiesels by using the HHV of their
No of double fatty acid) [10] (fatty methy acid) [11]
bonds) ester) [2]
pure fatty acids or that of their methyl esters.
Sixty biofuels’ data collected from the literature are used to
C4:0 C4H8O2 33.90
C5:0 C5H10O2 35.47 verify the accuracy of this method.
C6:0 C6H12O2 35.25 32.11
C7:0 C7H14O2 36.87
C8:0 C8H16O2 37.58 34.68 2. Materials and method
C10:0 C10H20O2 38.65 36.46 35.26
C12:0 C12H24O2 40.25 37.83 36.79
To calculate the HHV of vegetable oils, fats and biodiesels with
C12:1 C12H22O2 37.38
C14:0 C14H28O2 38.87 37.96
the HHV of the pure fatty acids or that of their methyl esters the
C14:1 C14H26O2 38.39 following relation (1) is used:
C16:0 C16H32O2 43.27 39.41 38.87
X .X
C16:1 C16H30O2 39.26
HHVc ¼ xi Ai xi (1)
C18:0 C18H36O2 44.25 40.03 39.61
C18:1 C18H34O2 45.96 39.87 39.32
C18:2 C18H32O2 44.57 39.66 where xi is the mass fraction (or weight percent) of fatty acid i, Ai is
C18:3 C18H30O2 41.53 39.30 the HHV of the pure fatty acid i or that of the pure fatty acid methyl
C20:0 C20H40O2 40.58 ester i; HHVc is the HHV of the vegetable oil, the fat or that of the
C20:1 C20H38O2 40.61 biodiesel.
C22:0 C22H44O2 41.03
C22:1 C22H42O2 40.95
To verify the previous relation, the values of xi in Eq. (1) are
obtained from the data of the sixty biofuels collected from the
literature with their fatty acid composition and their HHV.
Ai will be calculated from the experimental values reported by
Freedman et al. [1], Sadrameli et al. [10] and those reported by
Knothe [11]. As it is difficult to get the experimental HHV of all

Table 2
Higher heating values (HHV in MJ/kg) calculated with the different equations established for the fatty acids encountered in the biofuels studied.

Fatty acid name Chemical Chemical Molecular Molecular HHV of methyl HHV of pure HHV of pure HHV of pure HHV of pure
(carbon chain: formula of formula weight of weight of ester from fatty acid from fatty acid from fatty acid from fatty acid from
No of double bonds) fatty acid of fatty acid fatty acid fatty acid Eq. (4) Eq. (2) Eq. (5) (Demirbas) Eq. (3) (Knothe) Eq. (8)
methyl ester (g/mol) methyl ester (Freedman (Sadrameli (Fassinou et al.)
(g/mol) and Bagby) et al.)
Caproic acid (C6:0) C6H12O2 C7H14O2 116.16 130.19 33.09 35.87 29.63 33.55 30.25
Capryric acid (C8:0) C8H16O2 C9H18O2 144.21 158.24 34.71 37.20 33.48 34.57 33.42
Capric acid (C10:0) C10H20O2 C11H22O2 172.27 186.30 36.06 38.58 36.08 35.60 35.55
Lauric acid (C12:0) C12H24O2 C13H26O2 200.32 214.35 37.22 40.02 37.95 36.62 37.09
Myristic acid (C14:0) C14H28O2 C15H30O2 228.38 242.40 38.24 41.50 39.36 37.65 38.25
Palmitic acid (C16:0) C16H32O2 C17H34O2 256.43 270.46 39.14 43.04 40.46 38.67 39.16
Palmitoleic acid C16H30O2 C17H32O2 254.41 268.44 39.08 42.93 38.89 38.60 38.51
(C16:1)
Heptadecanoic acid C17H34O2 C18H36O2 270.46 284.48 39.56 43.84 40.92 39.18 39.54
(C17:0)
Heptadecanoic Acid C17H32O2 C18H34O2 268.44 282.47 39.50 43.72 39.44 39.11 38.93
(C17:1)
Stearic acid (C18:0) C18H36O2 C19H38O2 284.48 298.51 39.96 44.64 41.34 39.69 39.89
Oleic acid (C18:1) C18H34O2 C19H36O2 282.47 296.50 39.90 44.53 39.94 39.62 39.31
Ricinoleic acid C18H35O3 C19H37O3 299.48 313.50 40.37 45.52 40.48 40.24 36.81
(C18:1OH)
Linoleic acid (C18:2) C18H32O2 C19H34O2 280.45 294.48 39.85 44.41 38.51 39.55 38.72
Linolenic acid (C18:3) C18H30O2 C19H32O2 278.44 292.46 39.79 44.29 37.07 39.47 38.12
Arachidic acid (C20:0) C20H40O2 C21H42O2 312.54 326.57 40.70 46.30 42.07 40.72 40.49
Gadoleic acid (C20:1) C20H38O2 C21H40O2 310.52 324.55 40.65 46.18 40.80 40.64 39.96
Eicosadienoic acid C20H36O2 C21H38O2 308.51 322.53 40.60 46.06 39.51 40.57 39.43
(C20:2)
Eicosatetraenoic acid C20H32O2 C21H34O2 304.47 318.50 40.50 45.82 36.87 40.42 38.35
(C20:4)
Eicosapentaenoic acid C20H30O2 C21H32O2 302.46 316.49 40.44 45.70 35.53 40.35 37.80
(C20:5)
Behenic acid (C22:0) C22H44O2 C23H46O2 340.59 354.62 40.39 48.02 42.68 41.74 40.98
Docosenoic acid (C22:1) C22H42O2 C23H44O2 338.58 352.60 41.34 47.90 41.51 41.67 40.51
Docosatetraenoic acid C22H36O2 C23H38O2 332.53 346.56 41.20 47.52 37.93 41.45 39.04
(C22:4)
Docosapentaenoic acid C22H34O2 C23H36O2 330.51 344.54 41.15 47.40 36.71 41.37 38.54
(C22:5)
Docosahexaenoic acid C22H32O2 C23H34O2 328.50 342.52 41.10 47.27 35.47 41.30 38.03
(C22:6)
Lignoceric (C24:0) C24H48O2 C25H50O2 368.65 382.67 42.02 49.81 43.19 42.77 41.41
Nervonic acid (C24:1) C24H46O2 C25H48O2 366.63 380.66 41.97 49.67 42.12 42.69 40.97
800 W.F. Fassinou / Energy 45 (2012) 798e805

Table 3
(aed) Fatty acid composition (wt %) of the biofuels studied.

Fatty acid 1-Corn 2-Cottonseed 3-Crambe 4-Linseed 5-Peanut 6-Rapeseed 7-safflower 8-Sesame 9-Soya 10-Sunflower 11-Canola 12-Crude 13-Linseed
oil oil oil oil oil oil oil oil bean oil oil oil Balanites oil
oil (CBO)
C6:0
C8:0
C10:0
C12:0
C14:0
C16:0 12 28 2 5 11 3 9 13.1 12 6.4 4 17.0 5.1
C16:1 0.1 4.3 0.3
C17:0
C17:1 3.9
C18:0 2 1 1 2 2 1 2 3.9 3 2.9 2 7.8 2.5
C18:1 25 13 19 20 48 64 12 52.8 23 17.7 60 32.4 18.9
C18:1OH 18.1
C18:2 6 58 9 18 32 22 78 30.2 55 72.9 20 31.2 55.1
C18:3 7 55 1 8 0 6 10 7.2
C20:0 2 1 0 0 0
C20:1
C20:2
C20:4
C20:5
C22:0 0 0 1 2
C22:1 0 0 59 0
C22:4
C22:5
C22:6
C24:0 1 1
Total ¼ TFA 45 100 101 100 98 98 101 100 99 100 96 100 100
Ref. [13] [13] [13] [13] [13] [13] [13] [13] [13] [13] [14] [15] [16]

Fatty acid 14-Jatropha 15-Putranjiva 16-Coconut 17-Palm 18-Cotton 19-Rice 20-Jatroba 21-Crude 22-Palm 23-Waste 24-Animal 25-Pumpkin
curcas oil roxburghii oil kernel oil seed oil Bran oil oil Soybean oil (PO) cooking oil fat (AF) seed oil
non-edible oil oil (SBO) (WCO) methyl ester
C6:0 0.39
C8:0 5.75 3.77
C10:0 5.09 3.67
C12:0 44.56 48.38 0.01
C14:0 0.05 0.03 19.08 17.37 0.07 0.99 0.22 3.14 0.11
C16:0 14.7 10.23 10.04 9.13 28.7 14.8 4.2 10.47 43.03 9.28 29.06 12.51
C16:1 0.65 0.07 0.3 14.2 0.1 0.19 0.49 3.32 0.15
C17:0 0.07 0.08 0.1 0.07 1.07 0.08
C17:1 0.02 0.04
C18:0 6.75 10.63 3.57 2.72 0.9 1.9 6.9 3.34 4.31 3.95 23.82 5.43
C18:1 40.05 48.65 8.8 12.56 13 45.2 43.1 24.96 39.47 54.55 35.92 37.07
C18:1OH
C18:2 36.6 27.50 2.72 2.4 57.4 34.2 34.3 53.28 10.82 29.67 1.8 43.72
C18:3 0.15 0.87 6.46 0.29 0.25 0.54 0.18
C20:0 0.15 1.05 0.39
C20:1 0.3 0.11
C20:2
C20:4
C20:5
C22:0 0.1 0.24 0.12
C22:1 0.03 0.02
C22:4
C22:5
C22:6
C24:0 0.31 0.06
Total ¼ TFA 99.2 100 100 100 100 96.4 102.7 98.76 99.2 98.48 98.67 100
Ref [17] [18] [19] [19] [20] [20] [20] [21] [21] [21] [22] [23]

Fatty acid 26-Biodiesel 27-Methyl ester 28-Sunflower 29-Rapeseed 30-Olive 31-Used 32-Biodiesel 33-Soybean 34-Soybean 35-Yellow 36-Ethyl-
from waste of used oil ethyl oil ethyl oil ethyl frying oil from soybean methyl ester methyl ester grease methyl soy
cooking oil vegetable oil esters esters esters ethyl esters oil A (SMEA) B (SMEB) ester (YGME)
C6:0
C8:0
C10:0
C12:0 1.98
C14:0 0.54 1.53 0.08 1.27
C16:0 14.18 54.76 6.2 4.9 11.6 15.65 10.76 10.49 10.81 17.44 5.2
C16:1 0.74 0.1 0.9 0.31 0.12 0.11 2.03
C17:0 0.17
C17:1
C18:0 3.77 6.9 3.7 1.6 3.1 3.1 4.37 4.27 4.54 12.38 6.1
C18:1 47.51 36.23 25.2 33.0 74.98 29.57 24.13 24.20 24.96 54.67 10.6
 W.F. Fassinou / Energy 45 (2012) 798e805 801

Table 3 (continued )

Fatty acid 26-Biodiesel 27-Methyl ester 28-Sunflower 29-Rapeseed 30-Olive 31-Used 32-Biodiesel 33-Soybean 34-Soybean 35-Yellow 36-Ethyl-
from waste of used oil ethyl oil ethyl oil ethyl frying oil from soybean methyl ester methyl ester grease methyl soy
cooking oil vegetable oil esters esters esters ethyl esters oil A (SMEA) B (SMEB) ester (YGME)
C18:1OH
C18:2 24.83 3.57 63.1 20.4 7.8 41.53 51.83 51.36 50.66 7.96 18.59
C18:3 4.97 0.3 7.9 0.6 1.04 6.81 7.48 7.27 0.69
C20:0 0.80 0.36 0.37 0.25
C20:1 0.2 9.3 0.01 0.11 0.28 0.32 0.52
C20:2 0.17
C20:4 0.38
C20:5 0.03
C22:0 0.10 0.7 0.1 0.24 0.40 0.42 0.21
C22:1 0.18 0.1 23.0 0.02 0.07
C22:4 0.14
C22:5 0.05
C22:6 0.04
C24:0 0.2 0.5 0.30 0.14 0.12
Total ¼ TFA 98.6 99.99 99.8 100.1 99.59 93.85 97.9 99.25 99.58 97.42 40.49
Ref. [24] [25] [26] [26] [26] [26] [27] [27] [28] [28] [29]

Fatty acid 37-M- 38-Canola 39-Biodiesel 40-Soybean 41-Peanut 42-Corn oil 43-Sunflower 44-Rapeseed 45-Palm 46-Palm 47-Waste
Soy oil from soybean oil methyl oil methyl methyl ester oil methyl ester oil methyl oil methyl kernel oil fried oil
oil ester (SOME) ester (PNOME) (COME) (SFOME) ester (ROME) ester (POME) methyl ester methyl ester
(PKOME) (WFOME)
C6:0
C8:0 3.6
C10:0 3.1
C12:0 0.2069 0.5 48 1.6
C14:0 0.7091 1.6 14.7 1.5
C16:0 16.3 4 15.256 11.7 17.2 11.4 4.9 5.2 49.8 11.5 27.3
C16:1 0.799
C17:0 8.8963
C17:1
C18:0 6.0 2 3.921 3.97 2.7 1.3 2.3 1.4 2.9 1.4 4.9
C18:1 24.3 60 17.8306 21.27 40.5 27.1 32.6 66 38.6 15.9 36.1
C18:1OH
C18:2 53.4 20 34.4505 53.7 36.6 60.2 59.4 18.9 6.6 1.8 25.7
C18:3 10 4.6716 8.12 0.5 5.6 1.9
C20:0 0.3524 1.23 0.9 1.9
C20:1 0.3841
C20:2
C20:4
C20:5
C22:0 0.6506 1.5 0.5 1
C22:1 0.2179
C22:4
C22:5
C22:6
C24:0 0.2634
C24:1 1.1561
Total ¼ TFA 100 96.00 89.7655 99.99 99.9 100 99.7 100 100 100 99.00
Ref. [29] [14] [30] [31] [31] [31] [31] [31] [31] [31] [31]

Fatty acid 48-Refined 49-Soybean 50- 51-waste 52-Unused 53-Waste 54-Waste 55-Refined 56-Waste 57-Waste 58-Polanga 59-Jatropha 60-Mahua
cotton methyl ester Sunflower cooking sunflower cooking cooking rapeseed oil cooking cooking oil (calophyllum (jatropha oil
oil vegetable oil from (restaurants, oil ethyl ester inpphyllum) curcas)
oil hospitals hotels and methyl (WCOE)
domestic esters
sector) (WCOM)
C6:0
C8:0
C10:0
C12:0 0.08 0 0 0.08
C14:0 0.8 0.47 0.13 0.15 0.47 0.06 0.14 0.3
C16:0 25.7 8.8 5.1 13.64 7.47 10.89 13.64 4.72 10.54 11.03 12.01 16 22.0
C16:1 0.5 0.09 0.84 0.28 0.74 0.84 0.24 0.64 0.61
C17:0 0.13 0.068 0.09 0.13 0 0.09
C17:1 0.11 0.05 0.11 0.11 0.13 0.09
C18:0 2.4 4.55 2.8 5.72 4.07 4.45 5.72 3.01 4.02 4.64 12.95 6.5 22.5
C18:1 18.2 24.16 26.4 43.36 30.4 60.44 43.36 54.62 54.74 43.3 34.09 43.5 43.0
C18:1OH
C18:2 51.3 52.67 65.7 33.63 54.35 21.54 33.63 27.2 28.03 38.42 38.26 34.4 11.0
C18:3 0.3 7.74 0.58 1.74 0.36 0.58 7.14 0.29 0.36 0.3 0.8
C20:0 0.2 0.39 0.34 0.37 0.43 0.34 0.37 0.32 1.65
C20:1 0 0.23 0.57 0.39 0.4 0.57 0.44 0.29
C20:2
(continued on next page)
802 W.F. Fassinou / Energy 45 (2012) 798e805

Table 3 (continued )

Fatty acid 48-Refined 49-Soybean 50- 51-waste 52-Unused 53-Waste 54-Waste 55-Refined 56-Waste 57-Waste 58-Polanga 59-Jatropha 60-Mahua
cotton methyl ester Sunflower cooking sunflower cooking cooking rapeseed oil cooking cooking oil (calophyllum (jatropha oil
oil vegetable oil from (restaurants, oil ethyl ester inpphyllum) curcas)
oil hospitals hotels and methyl (WCOE)
domestic esters
sector) (WCOM)
C20:4
C20:5
C22:0 0 0.41 0.54 0.69 0.39 0.54 0.66 0.55
C22:1 0 0.01
C22:4
C22:5
C22:6
C24:0 0 0.13
C24:1 0.01
Total ¼ TFA 99.4 99.19 100.00 100.01 100.008 99.99 100.01 96.99 100.00 100.00 97.61 101.2 100.15
Ref. [32] [33] [34] [35] [35] [36] [36] [37] [38] [38] [39] [39] [40]

components of biofuels, some equations are deduced from the
previous data to obtain them. Therefore, with the various HHVs of
the fatty acids, the relation between HHV and MW are investigated
for the data of Freedman et al., Sadrameli et al. [10] and those
reported by Knothe [11], respectively. Among the possible equations,
only those which give values near the experimental ones are
selected: it is the case of Sadrameli et al (Eq. (2)), the values reported
by Knothe (Eq. (3)) and those of Freedman et al. (Eq. (4)). The
equations are then used to compute the HHV of the pure fatty acids
or that of their methyl esters required for the study. The equations
retained allow the simultaneous calculation of the saturated and
unsaturated fatty acids: generally, they are separated [2,10].
Ai ¼ 30:842 Exp ð0:0013 MWÞ R2 ¼ 0:9476
Ai ¼ 0:0365 MW þ 29:31 R2 ¼ 0:9732
Ai ¼ 8:277Ln ðMWÞ  7:2132 R2 ¼ 0:9701
For comparison, Ai will also be computed with the following
relation of Demirbas (5) and the correlation (8) already mentioned
12, 1 and 16 are the atomic weight of carbon, hydrogen and oxygen,
respectively.
The Ai obtained with Sadrameli et al., Knothe, Demirbas and
Fassinou et al. give the HHV of the pure fatty acids while those of
Freedman et al. those of their fatty acid methyl esters.
It must be noticed that Sadrameli et al., Knothe and Freedman
et al. data give the experimental HHV of the pure fatty acids or
methyl esters. Demirbas formula allows calculating the HHV of neat
acids by knowing their molecular weight and the number of their
double bonds. Fassinou et al.’s method allows the calculation of the
HHV of each pure fatty acid with their chemical formula. Demirbas
and Fassinou et al.’s formulae are used to verify or to compare the
values given by equations derived from the data of Sadrameli et al.,
(2) Knothe and Freedman et al.
The accuracy of the previous correlations is estimated by
(3) a comparison between the HHV predicted (HHVC) and the one
measured (HHVM). For this purpose, the average absolute error
(AAE) and the average bias error (ABE) are evaluated by using the
(4) formulae (12) and (13).
X
n

by Fassinou et al. in Ref. [8] for vegetable oils, animal fats and Average absolute errorðAAEÞ ¼ð1=nÞ jðHHVC  HHVM Þ
n¼1
biodiesels
=HHVM j  100ð%Þ ð12Þ
Ai ¼ 49:43  0:015IV  0:041SV (5)
IV and SV are the iodine value and the saponification value of the X
n

pure fatty acid, respectively. IV and SV are computed as below [12]: Average bias errorðABEÞ ¼ ð1=nÞ ½ðHHVC HHVM Þ=HHVM 
n¼1
IV ¼ 100ð253:51 dbÞ=MW (6) 100ð%Þ
(13)
SV ¼ 56; 106=MW (7)
HHVC and HHVM are the gross heating value of each data point
from calculation and experiment, respectively; n is the number of
Ai ¼ 34:03C þ 121:64H  12:54O (8)
data considered. HHVM is the experimental value generally given by
C, H and O are the mass fraction of the carbon, hydrogen and a bomb calorimeter.
oxygen, respectively, in the chemical formula of the fatty acid
whose chemical formula is CxHyOz. x, y and z are the number of
carbon, hydrogen and oxygen atoms in the chemical formula 3. Results and discussion
CxHyOz. C, H and O are calculated as follows:
In Table 1 are gathered the HHVs of the different pure fatty acids

.

C ¼ *
12 x 12* x þ 1* y þ 16* z (9) encountered in the literature. These values are used to establish the
Eqs. (2)e(4) from which some HHV in Table 2 are calculated.

.
 In Table 2, the different fatty acids which appear in the fuels
H ¼ 1* y 12* x þ 1* y þ 16* z (10) studied are listed with their molecular weight, their HHV calculated
with the relations derived from the values of Table 1, the correla-
tions of Demirbas (Eq. (5)) and Fassinou et al. (Eq. (8)); the HHV of

.

their pure fatty acid methyl ester is also present. As it can be seen,
O ¼ 16* z 12* x þ 1* y þ 16* z (11)
the values given by the relations of Demirbas, Fassinou et al.,
Table 4
Higher heating value (HHV in MJ/kg) and their absolute error (%) of the biofuels studied.

No ser-vegetable oil, fat or biodiesel HHVM HHVc Absolute error

Bomb Fassinou et al. Sadrameli et al. Demirbas Freedmand Knothe Fassinou et al. Sadrameli et al. Demirbas Freedmand Knothe
calometer and Bagby and Bagby
1-Corn oil 39.5 39.22 44.12 39.95 39.70 39.36 0.72 11.70 1.14 0.50 0.35
2-Cottonseed oil 39.5 38.93 44.05 39.27 39.66 39.31 1.44 11.51 0.58 0.40 0.48
3-Crambe oil 40.5 39.94 46.56 40.66 40.77 40.86 1.39 14.97 0.39 0.66 0.88
4-Linseed oil 39.3 38.56 44.31 38.16 39.79 39.48 1.90 12.74 2.91 1.26 0.46
5-Peanut oil 39.8 39.17 44.47 39.64 39.86 39.58 1.59 11.72 0.40 0.15 0.56
6-Rapeseed oil 39.7 39.08 44.44 39.41 39.86 39.56 1.56 11.93 0.72 0.40 0.34
7-Safflower oil 39.5 38.85 44.31 38.91 39.79 39.48 1.64 12.17 1.49 0.74 0.05
8-Sesame oil 39.3 40.65 46.01 41.17 41.33 41.00 3.44 17.07 4.76 5.17 4.33
9-Soya bean oil 39.6 38.91 44.27 39.08 39.78 39.46 1.74 11.80 1.32 0.44 0.36
10-Sunflower oil 39.6 38.89 44.35 38.97 39.82 39.51 1.80 11.99 1.59 0.54 0.24
11-Canola oil 40.64 39.07 44.42 39.39 39.85 39.55 3.87 9.30 3.07 1.94 2.68
12-Crude Balanites oil (CBO) 39.84 38.99 44.12 39.40 39.68 39.35 2.14 10.74 1.10 0.41 1.24
13-Linseed oil 39.84 38.54 44.57 39.31 39.92 39.64 3.27 11.86 1.33 0.19 0.50
14-Jatropha curcas oil 39.00 38.43 44.43 40.58 39.82 39.54 1.46 13.92 4.04 2.09 1.40
15-Putranjiva roxburghii 39.58 39.21 44.40 39.77 39.84 39.54 0.95 12.17 0.46 0.64 0.11
non-edible oil
16-Coconut oil 38.43 37.54 41.03 38.40 37.79 37.29 2.31 6.78 0.09 1.66 2.96

W.F. Fassinou / Energy 45 (2012) 798e805

17-Palm kernel oil 38.59 37.68 41.19 38.54 37.91 37.40 2.36 6.74 0.13 1.76 3.08
18-Cotton seed oil 39.40 38.93 44.04 39.28 39.65 39.31 1.18 11.76 0.30 0.64 0.24
19-Rice Bran oil 38.60 39.09 44.26 39.54 39.77 39.45 1.26 14.65 2.43 3.02 2.19
20-Jatroba oil 39.70 39.03 44.21 39.43 39.74 39.42 1.68 11.37 0.67 0.11 0.71
21-Crude Soybean oil (SBO) 38.82 38.92 44.29 39.08 39.79 39.47 0.25 14.09 0.68 2.49 1.67
22-Palm oil (PO) 39.11 39.19 43.84 40.05 39.55 39.18 0.21 12.11 2.43 1.14 0.19
23-Waste cooking oil (WCO) 38.94 39.13 44.34 39.60 39.81 39.50 0.49 13.87 1.70 2.23 1.44
24-Animal fat (AF) 38.75 39.33 43.96 40.35 39.61 39.25 1.49 13.43 4.11 2.21 1.30
25-Pumpkin seed oil methyl ester 38.08 39.07 44.31 39.46 39.79 39.48 2.60 16.35 3.64 4.49 3.67
26-Biodiesel from waste cooking oil 40.11 39.10 44.29 39.56 39.78 39.46 2.52 10.41 1.38 0.83 1.61
27-Methyl ester of Used vegetable oil 39.44 39.23 43.72 40.25 39.49 39.10 0.51 10.86 2.05 0.13 0.85
28-Sunflower oil ethyl esters 38.60 38.96 44.40 39.14 39.84 39.54 0.94 15.04 1.40 3.21 2.44
29-Rapeseed oil ethyl esters 38.30 39.43 45.34 39.91 40.25 40.11 2.96 18.39 4.20 5.08 4.74
30-Olive oil ethyl esters 38.20 39.26 44.36 39.92 39.82 39.51 2.78 16.13 4.51 4.23 3.44
31-Used frying oil ethyl esters 37.80 38.99 44.16 39.38 39.71 39.38 3.15 16.82 4.19 5.04 4.18
32-Biodiesel from soybean oil 39.77 38.92 44.29 39.10 39.79 39.47 2.12 11.38 1.67 0.05 0.75
33-Soybean methyl ester A (SMEA) 39.77 38.94 44.33 39.12 39.80 39.49 2.10 11.45 1.63 0.07 0.71
34-Soybean methyl ester B (SMEB) 39.96 38.95 44.33 39.15 39.80 39.49 2.53 10.92 2.03 0.40 1.17
35-Yellow grease methyl ester (YGME) 40.12 39.28 44.21 40.06 39.74 39.42 2.10 10.20 0.15 0.95 1.75
36-Ethyl-Soy 40.02 39.11 44.30 39.56 39.79 39.48 2.28 10.70 1.14 0.57 1.36
37-Methyl-Soy 39.84 39.00 44.23 39.35 39.75 39.43 2.09 11.03 1.23 0.21 1.02
38-Canola oil 39.70 39.07 44.42 39.39 39.85 39.55 1.59 11.89 0.77 0.38 0.37
39-Biodiesl from soybean oil 41.43 39.07 44.24 39.54 39.74 39.43 5.69 6.77 4.55 4.07 4.83
40-Soybean oil methyl ester (SOME) 39.66 38.92 44.30 39.08 39.79 39.47 1.87 11.69 1.46 0.32 0.47
41-Peanut oil methyl ester (PNOME) 39.70 39.11 44.30 39.59 39.78 39.47 1.48 11.58 0.28 0.21 0.57
42-Corn oil methyl ester (COME) 39.97 38.94 44.29 39.16 39.78 39.47 2.56 10.81 2.03 0.46 1.25
43-Sunflower oil methyl ester (SFOME) 39.95 38.97 44.40 39.16 39.84 39.54 2.45 11.15 1.98 0.27 1.02
44-Rapeseed oil methyl ester (ROME) 39.90 39.17 44.48 39.62 39.88 39.59 1.83 11.49 0.69 0.05 0.77
45-Palm oil methyl ester (POME) 39.91 39.18 43.71 40.13 39.48 39.10 1.82 9.53 0.54 1.07 2.04
46-Palm kernel oil methyl ester (PKOME) 38.53 37.74 41.30 38.60 37.98 37.47 2.05 7.19 0.18 1.44 2.74
47-Waste fried oil methyl ester (WFOME) 39.68 39.07 43.97 39.69 39.61 39.26 1.54 10.81 0.01 0.17 1.06
48-Refined cotton 38.60 38.97 44.06 39.36 39.66 39.32 0.96 14.15 1.97 2.77 1.87
49-Soybean methyl ester 39.84 38.93 44.35 39.09 39.81 39.51 2.28 11.33 1.87 0.07 0.83
50-Sunflower oil 39.71 38.93 44.38 39.07 39.83 39.53 1.96 11.75 1.62 0.30 0.47
51-Waste cooking vegetable oil 39.52 39.12 44.29 39.61 39.78 39.47 1.01 12.07 0.22 0.66 0.13
52-Unused sunflower oil 39.69 39.00 44.38 39.24 39.83 39.53 1.74 11.82 1.14 0.35 0.41

803
(continued on next page)
804 W.F. Fassinou / Energy 45 (2012) 798e805

Freedman et al. and Knothe are generally in a narrow range

Knothe
whereas Sadrameli et al.’s values are far from the others. Sadrameli

0.18
0.13

0.87
0.65
0.04
0.60
2.46
3.81
1.38
et al.’s values are higher than the others: probably because of the
experimental conditions. Thus the accuracy on the HHV determi-

Freedmand
nation of the pure fatty acids or that of their methyl esters influ-

and Bagby
ences the accuracy of the biofuel’s HHV obtained from these data.

0.59
0.66

1.64
1.42
0.82
1.39
3.29
3.03
1.36
Table 3aee gives the fatty acid composition (xi) and the total
percentage of all fatty acids detected and quantified (TFA) of the
biofuels used to verify the relation (1). The selection of the fuels is
Demirbas

0.45 based on the fact that their HHV and their fatty acid composition
0.22

0.49
1.03
0.10
0.95
2.87
1.84
1.57
must be given in the literature; their HHV generally estimated by
the bomb calorimeter method, is considered as the reference value
for the error evaluation.
Sadrameli et al.

As it can be seen in this table, fatty acids are the main compo-
nents of vegetable oils, fats and biodiesels. The most predominant
fatty acids encountered in this table are: palmitic (C16:0), stearic
12.07
12.07

7.91
13.27
13.00
12.29
12.90
14.96

12.04
(C18:0), oleic (C18:1), linoleic (C18:2), linolenic (C18:3); the other
fatty acids are not present in all oils but only in some of them and
their percentage varies according to their own particularity. As
Absolute error

Fassinou et al.

illustrated in Table 4, these five basic fatty acids’ HHV must be

obtained with the highest accuracy as possible because of their
effect on the heating value of the fuels studied.
0.97
1.01

0.35
0.26
0.97
0.30
1.59
4.00
1.82

Table 4 shows the various HHVs obtained by the bomb calo-

rimeter method and those computed from the combination of Eq.
Knothe

(1) with the Eqs. (2)e(4), the formulae of Demirbas (Eq. (5)) and
39.51
39.47

39.54
39.51
39.49
39.48
39.45
39.44
39.41

Fassinou et al. (Eq. (8)), respectively. Their error evaluation appears

also in this table. The HHV obtained with the correlations of
Freedmand

Demirbas, Fassinou et al, Freedman et al. and Knothe are around

and Bagby

39 MJ/kg (39e40 MJ/kg) which is consistent with the experimental

39.81
39.78

39.84
39.82
39.80
39.80
39.77
39.76
39.72

values and those encountered in the literature. The values calcu-

lated with the data of Sadrameli et al. are around 44 MJ/kg which is
far from those provided by the experimental method but near of
Demirbas

the HHV of Diesel fuels. This discrepancy of Sadrameli et al.’s data

39.76
39.61

39.39
39.66
39.52
39.62
39.60
40.25
39.49

with the others would explain the difference which has appeared in
the HHVs. Therefore Sadrameli et al.’s data can not be recom-
mended for the applicability of the correlation (1) to the fuels
Sadrameli et al.

studied here.
From the results obtained, it must be noted that the heating
value of the pure fatty acids or that of their methyl esters can be
44.35
44.29

44.40
44.36
44.33
44.31
44.26
44.24
44.19

used to calculate the HHV of the fuels studied: the difference

between the values given by Freedman et al.’s data (HHV of fatty
acid methyl esters) and those of Knothe, Demirbas and Fassinou
Fassinou et al.

et al. (HHV of pure fatty acids), is negligible.

The average absolute errors are: 1.57, 1.39, 1.38, 1.82 and 12.04%
39.12
39.19

39.06
39.16
39.10
39.13
39.11
39.36
39.02
HHVc

for: Demirbas, Freedman et al., Knothe, Fassinou et al. and Sadra-

meli et al., respectively. The average bias errors (not reported in
Table 4) are 0.13, 0.71, (0.09), (1.08) and 12.04% for: Demirbas,
calometer

Freedman et al., Knothe, Fassinou et al. and Sadrameli et al.,

HHVM

Bomb

respectively.
39.52
39.58

39.20

39.45
39.26
39.48
39.25
38.50
41.00

These error values show the merits, the applicability and the
validity of using the HHV of neat fatty acids and methyl esters to
56-Waste cooking oil Methyl esters (WCOM)

calculate the HHV of vegetable oils, fats and biodiesels.

53-Waste cooking collected from hospitals

The previous method is applied to sixty biofuels coming from

57-Waste cooking oil Ethyl ester (WCOE)
58-Polanga (calophyllum inpphyllum)

different laboratories of the world; the HHVs obtained are consis-

No ser-vegetable oil, fat or biodiesel

54-Waste cooking from restaurants,

tent with the experimental ones. Therefore the results of this study
can be used to predict the heating value of any vegetable oil, fat and
hotels and domestic sector

59-Jatropha (jatropha curcas)

biodiesel independently of its origin.

55-Refined rapeseed oil
Table 4 (continued )

4. Conclusion
Average value
60-Mahua oil

In this paper the HHV of vegetable oils, fats and biodiesels is

calculated by using the HHV of their pure fatty acids or that of
their methyl esters. The results show that using the relation
P P
HHVc ¼ ( xiAi)/ xi (1) to obtain the HHV of the biofuels (HHVc)
 W.F. Fassinou / Energy 45 (2012) 798e805
depends strongly on the accuracy put on the determination of the
HHV of the pure fatty acids (Ai) or on that of their methyl esters.
An absolute error inferior to 2% shows the good agreement
existing between the experimental HHVs and those computed
using this method.
Further investigations must be done to determine experimen-
tally the HHV of all neat fatty acids or methyl esters which
constitute the biofuels; they can help compute the HHV of biofuels
with a greatest accuracy.
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