Fuel Processing Technology 152 (2016) 399–405

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Fuel Processing Technology

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Research article

Modification of Dulong's formula to estimate heating value of gas, liquid

and solid fuels
Sou Hosokai ⁎, Koichi Matsuoka, Koji Kuramoto, Yoshizo Suzuki
National Institute of Advanced Industrial Science and Technology, 16-1, Onogawa, Tsukuba, Ibaraki 305 8569, Japan

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

Article history: Estimation equations for determining the heating value of hydrocarbon fuels were evaluated. Several types of es-
Received 22 March 2016 timation equations were proposed so far to determine the heating value on the basis of the elemental composi-
Received in revised form 27 June 2016 tion. The estimation equations were used to evaluate the elemental composition and the heating value of 406
Accepted 28 June 2016
standard gaseous organic compounds. As a result of the evaluation, Dulong's formula was appropriate for esti-
Available online 6 July 2016
mating the heating value; however, only a limited range of heating values can be determined, because Dulong's
Keywords:
formula was developed for determining heating value of coals, which have unidentified structures. Another rea-
Heating value son for the limitation was that the effect of latent heat. Therefore, Dulong's formula were modified with the lower
Elemental composition heating values (LHV) of 406 standard gaseous organic compounds, which have identified structures, to obtain the
Biomass following modified formula taking latent heat into account:
Coal © 2016 Elsevier B.V. All rights reserved.
Bio-oil
Estimation equation

LHV [kJ/g] = 38.2mC + 84.9 (mH – mO/8) – ΔHlwhere mC, mH, and mO
were the contents of carbon, hydrogen, and oxygen, respectively, on
any (wet, dry or ash free) bases. ΔHl described latent heat. When the
equation applied to gas, liquid and solid fuels, ΔHl should be 0, 0.5 and
0.62 kJ/g, respectively. The modified formula was applied to LHV esti-
mation of liquid and solid fuels. 90 liquid fuels, produced from biomass
pyrolysis, and 770 coals were investigated with the modified Dulong's
formula. The modified Dulong's formula well described the reported
heating values of 90 liquid fuels and 770 coals having LHV ranging
from 10 to 40 kJ/g. Therefore, the modified Dulong's formula can be ap-
plied to gas, liquid and solid fuels.
1. Introduction
Heating value is an important property that is used to evaluate the
fuel quality. In practice, the heating value of a fuel is measured with
bomb calorimetry based on standard methods such as ASTM-D2015.
Another method to evaluate the heating value is the use of estimation
equations. Several kinds of estimation equations have been reported,
such as those based on the ultimate analysis (or elemental composition)
[1–4], proximate analysis [1,4,5], and chemical composition [1,2,6].
Since a fuel produces heat owing to the recombination of chemical
bonds between its elements, the estimation equation based on the ulti-
mate analysis should be the most accurate method among the proposed
estimation methods. Dulong's formula is one of the famous equations
⁎ Corresponding author.
E-mail address: sou.hosokai@aist.go.jp (S. Hosokai).
based on the ultimate analysis. This equation is often utilized for esti-
mating the coal heating value [7]. Dulong's formula can be used to ob-
tain the heating value of anthracitic, semi-anthracitic, and bituminous
coals with 1.5% error, compared to the values obtained using the oxy-
gen-bomb calorimeter [7]. However, it has been reported that the
values calculated by using the formula show some deviations from the
experimentally determined values for lignite and subbituminous coals
[7] because of their high oxygen content. Therefore, there must be a
limit for extrapolating the estimation equations, because almost all pro-
posed formulas are approximated by using the actual heating values of
coals, which indicates a narrow range of heating value around 30 kJ/g.
This means that the proposed formulas are only accurate around
30 kJ/g. Another reason is that almost all of the proposed formulas are
developed with coals, which have complex and unidentified structures.
To overcome the extrapolation limit of the estimation equations,
they should be optimized using the heating value of more general com-
pounds, which have identified structures. Yang et al. [8] estimated the
enthalpy of biomass-derived oil using standard enthalpies of hydrocar-
bon compounds in NIST library [9]. They proposed an estimation equa-
tion for determining the enthalpy of bio-oil with a polynomial
approximation of H/C and O/C. They showed that it is possible to expand
the extrapolation limit of the estimation equation by using the heating
value of standard materials, although the accuracy of the estimation
equation could not be confirmed.
In this research, we quantitatively confirmed the limitation of the es-
timation equations and proposed an estimation equation, modified
Dulong's formula, to determine heating values of various gas, liqud
and solid fuels. Then, the applicability of the modified Dulong's formula

http://dx.doi.org/10.1016/j.fuproc.2016.06.040
0378-3820/© 2016 Elsevier B.V. All rights reserved.
400 S. Hosokai et al. / Fuel Processing Technology 152 (2016) 399–405
to the heating values of liquid and solid fuels was confirmed by using
the reported heating values.
2. Applicability of estimation equations to gaseous fuels
2.1. Equations applied to estimation
Table 1 shows a list of equations for estimating the heating values re-
ported so far. Since the equations shown in the table were developed for
the determination of higher heating values (HHV), the equations were
modified for the determination of lower heating value (LHV) by
subtracting the heat of water vaporization (mH(MH2O/MH2)ΔHboil =
(18/2)∗ 2.44mH = 22.0mH), where mH, MH2O, MH2, and ΔHboil are the hy-
drogen content, molecular weight of water, molecular weight of hydro-
gen, and heat of water vaporization (2.44 [kJ/g]), respectively. For
Dulong's formula, 22.0 was subtracted from the coefficient of (mH −
mO/8) because the coefficient express the heating value of hydrogen.
The equations are divided into three groups: Groups I, II, and III. Group
I equations have a simple linear relationship. They are very simple,
and can be used to estimate the contribution of each element on the
heating value. Group II equations comprise Dulong-type equations,
and they assume that all of the oxygen in the fuel is associated with hy-
drogen. Therefore, the amount of combustible hydrogen is obtained by
subtracting it with the amount of oxygen. Although Group II equations
are similar to those of the first group, they are conceptually completely
different. In contrast, Group III equations are Schuster-type equations,
which are conceptually similar to Dulong-type equations. Schuster-
type equations assumed that all of the oxygen in the fuel is associated
not only with hydrogen but also with carbon. Therefore, the amount
of combustible carbon and hydrogen is obtained by subtracting it with
the amount of oxygen. These equations were evaluated based on the
heating values of standard materials to clarify the limitation of the
equations.
To evaluate the equations, heating values of 406 gaseous compounds
and their elemental composition were used (NIST Chemistry WebBook)
[9]. These compounds comprised only C, H, and O, and the carbon num-
ber varied from 1 to 9. The equations listed in Table 1 show that the con-
tribution of the S content is smaller than that of other elements.
Furthermore the content of S in hydrocarbon fuels is too small to discuss
the effect on the heating value. Therefore, the effect of S is neglected to
simplify the evaluation. Ash also affects the heating value due to its di-
lution effect. Usually ash components are in oxide phase and give little
effect on the heating value. Therefore, the effect of ash on the heating
value can be also neglected in the estimation of the heating value.
Heating value is evaluated as the lower heating value (LHV). Fuels
are usually utilized at more than 100 °C. At such a temperature, water
exists as steam. Hence, heat of water vaporization cannot be utilized.
Table 1
List of estimation equations for determining the lower heating values (LHVs) of hydrocar-
bon fuels.
Author Formula
Group 1 Simple linear relationship
Strache-Lant [10] LHV [kJ/g] = 34.1 mC′ + 121.4 mH′ − 15.3 mO′ + 10.5 mS′
D'Huart [11] LHV [kJ/g] = 33.9 mC′ + 121.5 mH′ − 12.7 mO′ + 9.3 mS′
Demirbus [6] LHV [kJ/g] = 33.4 mC′ + 117.7 mH′ − 15.6 mO′
Group 2 Dulong type
Dulong [7] LHV [kJ/g] = 33.8 mC + 122.3 (mH − mO/8) + 9.4 mS
Group 3 Schuster type
Schuster [12] LHV [kJ/g] = (106.4 + 0.149 mO) (mC/3 + mH − (mO −
mS)/8) − 22.0 mH
Grumell and Davies LHV [kJ/g] = (1.52 mH + 98.8) (mC/3 + mH − (mO − mS)/8)
[13] − 22.0 mH
mC′, mH′, mO′, mN′, and mS′: contents of carbon, hydrogen, oxygen, nitrogen, and sulfur on
dry basis, respectively.
mC, mH, mO, mN, and mS: contents of carbon, hydrogen, oxygen, nitrogen, and sulfur on any
(wet, dry or ash free) basis, respectively.
Therefore, the LHV must give more practical value than the higher
heating value (HHV).
2.2. Limitation of the estimation equations
This section discusses the limit of extrapolation of estimation equa-
tions reported by many researchers [6,7,10–13]. Fig. 1 shows the valida-
tion results of the estimation equations. Heating values calculated on
the basis of LHV obtained from each equation are plotted against the
LHVs of 406 compounds obtained from the NIST library [9]. Almost all
of the equations describe the reported value at around 30 kJ/g well.
This is because all the equations are modified to estimate the general
fuels with the heating value of around 30 kJ/g. This fact revealed that
these equations can be extrapolated only in a limited range of heating
values. In fact, these equations overestimate the heating values of
more than 30 kJ/g and underestimate those less than 20 kJ/g. In the
case of Dulong's formula, two assumptions were considered to estimate
the heating value. The first assumption is, as mentioned above, that all
the oxygen containing in the fuel is accompanied with hydrogen. The
second is that the coefficients are determined from pure carbon and hy-
drogen. The LHV of pure carbon (or graphite) and pure hydrogen are
32.8 kJ/g and 120 kJ/g, respectively. The second assumption, in particu-
lar, limits the extrapolation of the equation. The second assumption
means that the heat is produced only by the recombination of graphitic
C\\C and H\\H bonds. However, hydrocarbon fuels do not contain
H\\H bond; instead, they contain other bonding species, especially
C\\H bonds. For C\\H bonds, we have to consider the contribution of
both C and H on the heating value. However, it is difficult to theoretical-
ly determine the contribution of C and H on the heating value because
bonding energy is affected by the structure of the compounds. There-
fore, in this work, we tried to optimize the coefficients of the formula
as fitting parameters. Details of the optimization are discussed later.
Among the equations, Dulong, Schuster, and Grumell and Davies
equations show an important characteristic, i.e., the estimated LHV of
steam is zero. However, other equations, especially Group 1 equations,
estimated the heating value of steam as not zero. This characteristic in-
dicated that the elemental compositions not only on dry bases, but also
on wet bases or on ash free bases could be applied to the Dulong,
Schuster, and Grumell and Davies equations. It has been assumed that
in the case of Dulong's formula, all oxygen is associated with hydrogen.
This association is described as stoichiometric water formation reaction.
Therefore, the second term in Dulong's formula was described as fol-
lows:
mH =M H –mO =ðM O =2Þ ¼ mH –mO =8 ð1Þ
where mH, mO MH and MO are hydrogen contents, oxygen contents, mo-
lecular weight of H and molecular weight of O, respectively. The above
equation helps calculate the correct value of the LHV of steam. The
same term has also been included in the Schuster or Grumell and Davies
equations to estimate the LHV of steam. Furthermore, this type of equa-
tion also considers stoichiometric carbon dioxide formation reaction,
which helps estimate the LHV of carbon dioxide as zero. Therefore the
Schuster or Grumell and Davies equations was described as follows:
mC =ðMC =4Þ þ mH =M H −mO =ðMO =2Þ ¼ mC =3 þ mH −mO =8 ð2Þ
where mC and MC are carbon contents and molecular weight of C,
respectively.
Hence, this section confirmed the limit of extrapolation of estima-
tion equations and the reason for the limitation. We also found an im-
portant characteristic in the estimation of steam heating value.
Therefore, Dulong- or Schuster-type equation seems to be appropriate
for estimating the LHV. However, another assumption made in the
Schuster-type equation was not appropriate. The applicability of the as-
sumptions is discussed in the next section.
 S. Hosokai et al. / Fuel Processing Technology 152 (2016) 399–405
Fig. 1. Relationship between 406 reported LHVs and those estimated with each estimation equation. Bold dashed line shows accordance between the calculated LHV and those reported in
database. Normal dashed line shows ±10% error.
2.3. Evaluation of assumptions made for the estimation equations
In this section, we try to confirm the applicability of the following as-
sumptions made for estimating the LHV before modifying the
equations.
We assumed a simple relationship between the elemental composi-
tion and heating value of a fuel. We employed Group 1-type equations
and then modified the coefficients of each element to minimize the
sum of the absolute value of deviation between the LHVs estimated
with the equation and reported LHVs in NIST library [9]. Determination
was performed with a type of gradient method. The coefficients giving
minimum deviation were solved numerically. Fig. 2 indicates the rela-
tionship between the database LHV and the one estimated with the
modified equation. The following equation was obtained by the optimi-
zation of coefficients:
LHV ½kJ=g ¼ 38:8 mC þ 81:4 mH –11:4 mO
401
¼ 38:8 mC þ 81:4 ðmH –0:140 mO Þ ð4Þ
¼ 81:4 ð0:478 mC þ mH –0:140 mO Þ ð5Þ
All the equations expressed above gave the same LHV, but the ex-
pression was different. The Eq. (3) is the optimized estimation equation
in Group 1-type. The Eqs. (4) and (5) are rewritten expressions of the
Eq. (3) to Dulong-type and Shuster-type expressions, respectively. If
the assumptions made in the Dulong-type or Shuster-type equations
are correct, coefficients of mC and mO should be similar to 1/3 and 1/8,
respectively as described in the Eqs. (1) and (2). The second and third
equations showed that the coefficient for oxygen is 0.140, whose
value is very similar to 1/8. This fact indicates that hydrogen and oxygen
tend to have a stoichiometric relationship, as assumed in Dulong's for-
mula. In the database we employed, aldehydes, carboxylic acids, ethers,
ð3Þ and esters are included. Oxygen in such compounds is not directly
402 S. Hosokai et al. / Fuel Processing Technology 152 (2016) 399–405
Fig. 2. Optimization result of the coefficients of Group 1-type estimation equation. Bold
dashed line shows accordance between the calculated LHV and those reported in
database. Normal dashed line shows ±10% error.
associated with hydrogen. Despite such a chemical structure, oxygen
still has a stoichiometric relationship with hydrogen. The third equation
indicates that the coefficient of carbon is 0.478, which is far from 1/3.
This fact indicates that oxygen in the chemical structure does not have
a stoichiometric relationship with carbon. Therefore, the assumption
for Schuster-type equation is not appropriate. Hence, we can conclude
that only Dulong-type formula can be appropriate for estimating LHV.
Optimization of the coefficients is discussed in Section 3.2.
The modified equation of Group 1 type can be applied for LHV esti-
mation with a high accuracy in a wide range of heating values. However,
as mentioned above, the LHV of steam cannot be properly estimated
with this equation. In fact, the estimated LHV of steam is − 1.1 kJ/g,
not zero. This deviation of LHV surely leads to large deviation from the
actual LHV, especially when the fuel contains a large amount of water.
Therefore, the equation is applicable only when the fuel does not con-
tain water or the elemental compositions on moisture free basis are
available.
2.4. Modification of Dulong's formula to extend applicability
The coefficients of Dulong-type equations were modified with the
same database as available in the NIST library, as mentioned above.
The coefficients were determined to minimize the mean absolute differ-
ence between the LHVs in the database and those calculated from the
modified equation. The coefficients were obtained numerically with
the gradient method, as described in Section 2.3. Fig. 3 shows the rela-
tionship between the LHVs in the database and those estimated with
the modified Dulong's formula. The modified equation is as follows:
LHV ½kJ=g ¼ 38:2 mC þ 84:9 ðmH −mO =8Þ
Contribution of carbon on the LHV in the modified Dulong's formula
is higher while that of hydrogen is lower than the original Dulong's for-
mula. This fact indicates that the contribution of carbon on the LHV is
higher than graphitic carbon. This is because standard materials de-
scribed in the NIST library do not contain graphitic C\\C bond. Even
general fuels do not contain a large amount of graphitic C\\C bond.
The contribution of hydrogen on the LHV is lower than pure hydrogen.
Hydrogen does not exist in the form of H\\H bond either in standard
materials in NIST library or in general fuels. Therefore, these coefficients
should be more appropriate for estimating the LHV than that used in the
original Dulong's formula. However, this modified Dulong's formula
cannot estimate pure carbon and pure hydrogen, nor can it properly
estimate the LHV of some compounds such as olefins and peroxides.
We will discuss the reason for the limitation in the next section.
2.5. Effect of structure on the accuracy of the estimation equations
Here, we discuss the limitation of the estimation equations. Fig. 3
shows some large deviations from the estimated LHV. We chose com-
pounds that indicated more than 10% error; e.g., acetylene (C2H2), eth-
ylene oxide (C2H4O), dimethyl peroxide (C2H6O2), ethyl hydroperoxide
(C2H6O2), dioxybismethanol (C2H6O4), propyl hydroperoxide (C3H8O2),
bicyclo[1.1.0]but-1(3)-ene (C4H4), succinic anhydride (C4H4O3), and
(Z)-hexa-1,5-diyne-3-ene (C6H4). We categorized the compounds into
15 typical structures; double bond, triple bond, cyclic, aromatic ring,
3-membered ring, 4-membered ring, ether, ester, ketone, aldehyde, car-
bonate, carboxylic acid, alcohol, and peroxide. Some compounds were
categorized in more than 2 structures. For example, cyclobutanone
was categorized in cyclic, 4-membered ring, and ketone. Heterocyclic
compounds such as furan and pyran were categorized as ether and cy-
clic. Details can be seen in the Supplemental data in excel format.
Among these structures, triple bond, 3-membered ring, peroxide
tended to give a large deviation, more than 10% error, between the re-
ported and the estimated LHVs. Carbonate, carboxylic acid and anhy-
dride tended to give more than 5% error. Aromatic ring, ether, ester,
double bond, cyclic, ketone, aldehyde, 4-membered ring, alcohol did
not give a large deviation, less than 5% error. It is well known that cyclic
compounds with 3-membered ring are not stable owing to the distor-
tion of the structure. Peroxide and acetylene are known as explosive
materials and therefore unstable. Heating value of compounds having
such unstable structures is higher than that of the normal single bond.
In fact, LHVs of the compounds having unstable structures tended to
be underestimated with the modified Dulong's formula. Stable struc-
tures such as aromatic ring, ester, carbonate, carboxylic acid, and anhy-
dride, can also be a cause of deviation. LHVs of the compounds having
stable structures tended to be overestimated, although the deviation is
relatively small compared to those having unstable structures. There-
fore some attention has to be paid when the estimation equations are
employed to estimate the LHVs of the compounds with such stable or
unstable structures.
Although structures affected the LHVs, deviation between the re-
ported and the estimated LHVs was decreased as the number of carbon
increases. For example, di-tert-butyl peroxide (C8H18O2) only gave 3%
error in spite of the peroxide structure. This fact indicated that content
of the stable or unstable structures in the compound or even mixture
ð6Þ
Fig. 3. Evaluation result of the optimized Dulong's equation with 406 standard
compounds. Bold dashed line shows accordance between the calculated LHV and those
reported in database. Normal dashed line shows ±10% error.
 S. Hosokai et al. / Fuel Processing Technology 152 (2016) 399–405 403

Table 2
Summary of the accuracy of estimation equations.

Equation type Maximum absolute difference, kJ/g Mean absolute difference, kJ/g Maximum absolute error, % Mean absolute error, % Correlation coefficient, –

Group 1
Strache-Lant 9.2 1.3 43.0 3.9 0.9859
D'Huart 9.3 1.3 26.5 3.6 0.9845
Gumz 10.6 1.8 49.4 5.6 0.9895
Demirbus 10.1 1.4 48.6 4.6 0.9810

Group 2
Dulong 9.4 1.3 42.8 3.8 0.9854
Group 3
Schuster 9.0 1.2 29.6 3.6 0.9870
Grumell and Davies 13.0 1.9 47.6 5.6 0.9798

This study
Modified group 1 7.9 0.8 30.3 2.6 0.9920
Modified Dulong 8.2 0.8 24.7 2.6 0.9919

affects the LHV. Therefore, the LHV of the compounds containing much
amount of the stable or unstable structures must be estimated with
large errors. Fortunately, general fuels do not contain such unstable
structures. Hence, we do not need to take care of such structural prob-
lems while trying to estimate such fuels.
2.6. Summary of evaluation of the estimation equations
Table 2 summarizes the accuracy of the estimation equations, and
tabulates the maximum absolute difference, error of LHV, and correla-
tion coefficient. The absolute difference was calculated by subtracting
the estimated LHV from the reported LHV in the NIST library. The
error was calculated by dividing the absolute difference from the report-
ed LHV. The correlation coefficient statistically showed the correlation
between the estimated and reported LHVs. An equation with correlation
coefficient closer to 1 is more accurate. The summary given in Table 2
reveals that the modified Dulong's formula affords the lowest difference
and error. The correlation coefficient is closest to 1. Hence, we can con-
clude that the modified Dulong's formula is the most appropriate meth-
od for estimating LHV. In Section 3, we discuss the applicability of the
formula to real fuels.
3. Applicability of the modified DULONG'S formula
3.1. Application to liquid fuels
Here, we confirm the applicability of the modified Dulong's formula
to real fuels. To investigate the applicability of this equation in a wide
range of heating values, we applied it to estimate the LHV of liquid
fuels produced from biomass pyrolysis. It is known that the LHV of gen-
eral fuels such as coal can be properly estimated because its heating
value is around 30 kJ/g. At such an LHV range, any estimation equation
investigated in this research can be used to estimate the LHV of fuels
with low deviation. Liquid fuels produced from biomass pyrolysis con-
tain a large amount of oxygen and moisture [14], whose contents de-
pend on the pyrolysis condition and the feedstock. The LHV of the
produced liquid fuel therefore shows a wide range of heating value. To
compare the reported elemental composition and the heating value of
liquid fuels, we referred to 30 reports that investigate 90 types of bio-
oils [15–44]. The LHV of the liquid fuel was estimated based on the ele-
mental composition and the modified Dulong's formula. Generally, the
heating value reported in the literature is on HHV basis. Therefore, the
LHV was calculated by using the following equation:
LHV ½kJ=g ¼ HHV ½kJ=g−ðmH ðM H2O =MH2 Þ þ mmoist ÞΔHboil ½kJ=g ð7Þ
where MH2O, MH2, and ΔHboil are the molecular weight of water, molec-
ular weight of hydrogen, and heat of water vaporization (2.4 [kJ/g]),
respectively.
For the estimation of LHVs of liquid fuels, it was required to consider
the effect of heat of vaporization, since the 406 compounds obtained
from NIST library were in gas phase. 430 standard compounds in NIST
library [9] were investigated for estimation of the heat of vaporization.
The heat of vaporization did not show any clear trend with any element
composition. Therefore we employed average value of 0.5 kJ/g for the
heat of vaporization. Therefore the modified Dulong's formula for liquid
fuels was described as follows;
LHV ½kJ=g ¼ 38:2 mC þ 84:9 ðmH −mO =8Þ − 0:5 ð8Þ
Fig. 4 shows the evaluation result of the estimation equation. The re-
ported 90 LHVs are plotted against the LHV estimated with the modified

Fig. 4. Application of estimation equations for LHVs of 90 liquid fuels reported in literatures. Bold dashed line shows accordance between the calculated LHV and those reported in database.
Normal dashed line shows ±10% error.
404 S. Hosokai et al. / Fuel Processing Technology 152 (2016) 399–405
Table 3
Comparison of the accuracy between the original and modified Dulong's formulas.
Equation type Maximum absolute difference, kJ/g Mean absolute difference, kJ/g
Dulong 5.7 1.2
Modified Dulong 5.2 1.4
Dulong's formula and the original Dulong's formula. The modified
Dulong's formula well represents the reported LHVs, while the original
Dulong's formula showed a large deviation at low LHV ranges. As men-
tioned above, the original Dulong's formula tends to underestimate at
low LHV ranges owing to the overestimation of the contribution of oxy-
gen on the LHV. Table 3 shows the accuracy of both Dulong's formulas.
The correlation coefficient of the modified Dulong's formula is closer
to 1, in contrast to the original formula. Hence, the modified Dulong's
formula better represents the LHV than the original. The modified and
original equations showed almost comparable accuracy for the estima-
tion of liquid fuels. Some of the reported LHVs cannot be estimated pre-
cisely with any estimation equation. Because the constituents of the bio-
oil are similar to those of the standard materials in the NIST library, the
estimated LHVs showed more than 10% error probably owing to the ex-
perimental error in the elemental composition and/or the HHV analy-
ses. In other words, the modified Dulong's formula can be utilized to
validate the elemental composition and the heating value obtained
experimentally.
3.2. Application to solid fuels
Applicability of modified Dulong's formula to solid fuels was also
evaluated. From the database of COALQUAL [45], heating values of 770
coals were obtained. For the estimation of solid fuels, the heat of fusion
should be considered in the estimation equation. The heat of fusion for
252 compounds in the NIST library [9] was investigated, and was ob-
tained average value of 0.12 kJ/g. Therefore the modified Dulong's for-
mula for solid fuels was expressed as follows;
LHV ½kJ=g ¼ 38:2 mC þ 84:9 ðmH − mO =8Þ − ð0:5 þ 0:12Þ ð9Þ
Fig. 5 and Table 4 show the result of evaluation. Original Dulong's
formula showed better accuracy than modified Dulong's formula. Mod-
ified Dulong's formula showed over estimation with almost constant
deviation of 1.3 kJ/g at any heating value. This must be due to the effect
of latent heat. The estimation equation employed averaged latent heat
obtained from standard compounds. Therefore the latent heat was not
properly estimated in Eq. (9). When the latent heat was optimized to
1.9 kJ/g, mean absolute difference and mean error were obtained as
0.3 kJ/g and 4.1%, respectively. Original Dulong's formula showed over
estimation at the heating value of more than 30 kJ/g while showed
Fig. 5. Application of estimation equations for LHVs of 770 solid fuels reported in COALQUAL. Bold dashed line shows accordance between the calculated LHV and those reported in
database. Normal dashed line shows ±10% error.
Maximum absolute error, % Mean absolute error, % Correlation coefficient, –
24.8 5.9 0.9510
31.0 7.3 0.9596
under estimation at the heating value of less than 5 kJ/g. This is why
original Dulong's formula gave large maximum error compared to mod-
ified one, because original Dulong's formula gave larger deviation at
lower heating value.
The results showed that modified Dulong's formula comparable to
the original one and could be applied to even solid fuels when the latent
heat was considered in the estimation equation. It should be noticed
that the effect of S and ash were neglected in the modified Dulong's for-
mula. The maximum values of S and ash contents in the COALQUAL da-
tabase were 12.4 and 90.8 mass%, respectively. The Dulong's formulas
did not give large error to the estimated LHVs, in spite of the neglect
of S and ash contents. The formulas are applicable at least when the S
and ash contents are up to 12.4 and 90.8 mass%, although we need to
clarify the effect of S and ash on LHVs in the future work.
4. Conclusions
Applicability of the estimation equation for the heating value of fuels
was investigated with the heating value of 406 standard compounds
from the NIST library. Owing to the limitation of the applicability of
the reported estimation equation, optimization of Dulong's formula
was performed. Therefore the following modified Dulong's formula
was proposed taking the latent heat into consideration:
LHV [kJ/g] = 38.2 mC + 84.9 (mH − mO/8) − ΔHlwhere ΔHl de-
scribed latent heat. When the equation applied to gas, liquid and solid
fuels, ΔHl should be 0, 0.5 and 0.62 kJ/g, respectively. The modified
Dulong's formula well described the reported LHVs of 90 liquid fuels
produced by biomass pyrolysis and/or reforming only with elemental
composition. The mean estimation error was within 10%. Applicability
of the modified Dulong's formula to LHVs of 770 solid fuels was also
evaluated. Although the original Dulong's formula was more accurate
than the modified, the modified formula can be comparable to the orig-
inal Dulong's formula by optimizing the latent heat. Hence, the modified
Dulong's formula can be used to determine heating values of gas, liquid
and solid fuels by considering the latent heat.
Nomenclature
mC content of carbon on any basis
mH content of hydrogen on any basis
mO content of oxygen on any basis
mN content of nitrogen on any basis
 S. Hosokai et al. / Fuel Processing Technology 152 (2016) 399–405 405

Table 4
Comparison of the accuracy between the original and modified Dulong's formulas.

Equation type Maximum absolute difference, kJ/g Mean absolute difference, kJ/g Maximum absolute error, % Mean absolute error, % Correlation coefficient, –

Dulong 16.9 0.4 505.3 5.5 0.9913

Modified Dulong 17.7 1.3 269.1 10.1 0.9910

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