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Abstract. The energy yield from the combustion of fatty acids and the ATP yield of their oxidation
increases with the length of the acyl chain and decreases with unsaturation. Simple expressions describing
these relationships are compared with data from the literature, and expressions for the yield of ATP and
reducing equivalents are given. From these we derive the corresponding expressions for the oxidation of
triacylglycerol. These expressions are used to estimate the energy yields from the oxidation of selected fats
and oils of known composition.
Keywords: fatty acids, combustion, oxidation, ATP yield, reducing equivalents.
in the coefficients only because n can be regression lines for the liquid (fH0 = – (25.37
large. The combustion of FA yields ± 0.09)n – (432.4 ± 0.8), r2 = 0.999, p <
2(n ) p 0.001) and condensed FAs (fH0 = – (29.9 ±
H c FA n f H 0 (CO ) f H 0 (H 2 O)
2 2 0.2)n – (415 ± 3), r2 = 0.999, p < 0.001).
6n 2 p 4
f H 0 (O 2 ) f H 0 (FA)
4
(4)
0
where fH for O2(g), H2O(liq) and CO2(g) are
0 kJ mol-1, -285.83 kJ mol-1 and -393.51 kJ
mol-1, respectively[HOARE 1985, ATKINS 1990]. The
value used by nutritionists to express the
calorific value of foods is –Hc expressed on
a mass basis and so (3) can be used to correct
values expressed in kJ mol-1. Of course, after
collecting terms and using the constants, (4)
becomes
H c FA 679.34n 285.83 142.915 p (5)
f H 0 (FA)
and an empirical estimate of fH0(FA) can be Figure 2. Relationships between fH0 and
obtained using published data. for FAs. The solid lines are the regression
The values of –fH0(FA) increase lines for n = 18 (●: fH0 = (136 ± 7)n – (923 ±
with the number of methylene groups (Figure 12), r2 = 0.967, p < 0.001) and n = 5 (○: fH0
1) and decrease with each double bond = (121 ± 4)n – (558 ± 2), r2 = 0.991, p <
(Figure 2). Measurements of fH0(FA) for 0.001).
saturated FAs were obtained from seven
different sources and it is clear that there is f H 0 (FA) 25.8 0.2n 123 2 430 2 (6)
good agreement, whether in the liquid or 2
(r = 0.991, p < 0.001), indicating that
condensed state (Figure 1). The values for fH0(FA) changes by -25.8 kJ mol-1 per
methanoic acid (for which n = 1) are very methylene group, similar to the -25.3 kJ mol-1
similar, but do not lie on the regression line per methylene approached in the longer
through the remaining 77 values. The alkanes[ALBERTY & GEHRIG 1984].
presence of one or more double bonds makes Deprotonation of the FA has little
fH0(FA) less negative by about 130 kJ mol-1 effect on fH0(FA). For example, the
for each double bond (Figure 2). The enthalpy of the deprotonation of ethanoic acid
combined equation, obtained using multiple is only -0.41 kJ mol-1[GOLDBERG et al. 2002],
regression, is although the values surveyed by Goldberg et
al.[2002] ranged from -0.90 kJ mol-1 to +0.38 kJ
mol-1. The enthalpy of deprotonation of other
short chain FAs is no more than 3 kJ mole-
1[WILHOIT 1969, EBERSON 1969, SIMONETTA & CARRÀ 1969]
).
Incorporating the value for ethanoic acid into
(6) yields
f H 0 (FA) 25.8n 123 0.4 p 430 , (7)
where we have omitted the error estimates,
and substituting (7) into (5) yields an estimate
of the heat of combustion
H c FA 653.5n 163 143.3 p 430 . (8)
Expressions for fH0(FA)[AMEND &
HELGESON 1997, SIMONETTA & CARRÀ 1969, DUTT et al. 1992]
Figure 1. Relationship between fH0 and n >
or Hc [ADRIAANSE et al 1965, DUTT et al 1992, LIVESEY
1 for saturated FAs in liquid (○) and 1984]
corresponding to (7) and (8), respectively,
condensed (●) states. The solid lines are
4
Banat’s University of Agricultural Sciences and Veterinary Medicine from
Timisoara,
have been reported previously. Of these, that Hc(FA) approaches –46.6 kJ g-1 for long
only two[DUTT ET AL 1992, LIVESEY 1984] explicitly chain FAs (Figure 3). However, biologically
consider the effects of unsaturation, and one relevant FAs are heterogeneous mixtures in
of those[DUTT ET AL 1992] is based on the which n ranges up to about 24 and so
connectivity of the molecules rather than just combustion will yield less energy. Values of
n and . Equation (7) provides a better Hc can be estimated for mixtures of FAs
estimate of fH0(FA) (<R> = 2.8) than that of using
Dutt et al. [DUTT et al 1992] (<R> = 12.7) and it is
H c FA ,
the logical basis of (8). Equation (8) is a H c FA pFA (9)
slightly better estimator of Hc (<R> = 132.7) FA M FA
than that of Livesey[1984] (<R> = 151.2), and where p(FA) is the proportion of the mass
both are better than that of Dutt et al. [DUTT et al contributed by a particular FA. Combustion
1992]
(<R> = 168.0). In each case, the of the FAs from human fat or rattite or seed
expressions of Dutt et al. [DUTT et al 1992] deviate oils yields Hc 39.5 kJ g-1 despite quite
systematically from the data, especially for n different FA compositions (Table 1).
> 14.
According to (8), the effect of a Triacylglycerol combustion
double bond is to change Hc by +163 kJ Fatty acids are stored as
mole-1, similar to the prediction of triacylglycerols (TAGs) in which three FAs
Livesey[1984], but quite different from Dutt et are esterified to glycerol. Lipolysis involves a
al.[1992] according to whom it increases by 550 range of lipases [HIDE et al. 1992] catalysing
kJ mole-1. Comparison of the values of Hc hydrolytic reactions that release FAs. Of
for alkanes and the corresponding alkenes course, TAGs are highly heterogeneous
gives a value of about 115 kJ mole-1 per molecules, so the overall reaction depends on
double bond[ALBERTY & GEHRIG 1984, ALBERTY & the FA composition of the TAG, but the
GEHRIG 1985]
, and the data reported by mobilisation of TAG can be summarised as
Markley[1947] for three unsaturated FAs yield TAG 3H 2 O glycerol 3FA . (10)
an average value of 168 ± 8 kJ mole-1 per The combustion of glycerol (C3H8O3) can be
double bond. These data prompt the written
suggestion that the unsaturation correction in C 3 H 8 O 3 3.5O 2 3CO 2 4H 2 O (11)
(8) is more likely to be appropriate than is that
and, as there are three FAs per glycerol, the
inherent in the expression of Dutt et al.[1992].
combustion of one FA-equivalent of TAG
(FAeq) could be written
1 6n 2 p 4 7
C n H 2( n ) p O 2 C 3 H 8 O 3 O 2 .
3 4 6
2( n ) p 1
n 1CO 2 H 2 O
2 3
(12)
and so the enthalpy of combustion is
H c FA eq H c FA H c glyc f H 0 (H 2 O) .
1
3
(13)
Values of Hc can be estimated for TAGs
containing mixtures of FAs using
3H c FA 265.79 . (14)
Figure 3. Relationships between Hc and n H TAG
c p FA
FA 3M FA 38.016
for saturated FAs (●), unsaturated ( = 3) FAs
Combustion of the TAGs containing the same
() and FAeq (blue curve) . The horizontal FA composition as human fat or rattite or seed
dashed line indicates the limiting value of
oils yields, Hc 37-38 kJ g-1 despite the
Hc. different FA compositions (Table 1).
From (3) and (8), it will be apparent
5
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Table 1.
Calculated Hc and ATP yield of the oxidation of the FAs
and the corresponding TAGs of selected fats and oils.
Hc (kJ g-1) YATP (mol g-1)
FA TAG FA TAG
Human fat
neonate[Sarda et al. 1987] -39.2 -37.7 0.413 0.401
infant[Widdowson et al. 1975] -39.3 -37.8 0.413 0.401
adult[Jacobsen et al. 1983] -39.0 -37.6 0.410 0.399
Rattite oil
emu[Grompone et al. 2005] -39.4 -38.0 0.414 0.403
ostrich[Basuny et al. 2011] -39.3 -37.9 0.414 0.402
rhea[Grompone et al 2005] -39.3 -37.9 0.414 0.402
Seed oil
cotton[Arafat et al. 2011] -39.3 -37.9 0.413 0.401
semal[Arafat et al 2011] -39.4 -38.0 0.414 0.402
monsa[Arafat et al 2011] -39.4 -37.9 0.414 0.402
Figure 4. Energy yield from the oxidation of n-carbon FAs. The upper section represents the cycle
of -oxidation, the central section represents the operation of the TCA cycle and the bottom section
summarises the yield of NADH, UQH2 and GATP/ATP and the overall yield of ATP following the
oxidation of NADH and UQH2. The values given under oxaloacetate represent the yield of its
oxidation by the path described in the text.
7
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