Applied Thermal Engineering 26 (2006) 1492–1499

www.elsevier.com/locate/apthermeng

Effect of the gas state equation on the thermodynamic

diagnostic of diesel combustion
a,*
Magı́n Lapuerta , Rosario Ballesteros a, John R. Agudelo b

a
Escuela Técnica Superior de Ingenieros Industriales, University of Castilla—La Mancha, Edificio Politécnico,
Avda. Camilo José Cela, s/n. 13071 Ciudad Real, Spain
b
Grupo GASURE, Universidad de Antioquia, Colombia

Received 29 June 2005; accepted 3 January 2006

Available online 7 February 2006

Abstract

The effect of considering the gaseous fuel as ideal gas during the diagnostic procedure from experimental cylinder pressure signal from
a Diesel engine is analysed. After the chemical characterization of the fuel and the estimation of the thermodynamic properties, the com-
pressibility factor of the fuel was quantified under engine operating conditions, the prediction capability of four cubic state equations was
tested, and finally their application was extended to the whole gaseous mixture throughout the engine cycle. One of the tested equations
was finally selected and used to compare the main results of the combustion diagnostic procedure (mean cylinder temperature and heat
release) with those obtained with the ideal gas state equation, under two selected operating modes. Although the obtained differences are
relatively small, the deviations in the gas temperature around the top dead centre may be important in case that these results are used for
predictions of heat radiation and pollutant formation.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Diesel engines; Diesel fuel; Thermodynamics; State equations

1. Introduction taneous mean gas temperature throughout the combustion

The estimation of instantaneous temperature and heat
release along the compression and expansion stroke of
internal combustion engines has been and still is a common
practice as a final step of the combustion diagnostic meth-
ods. These methods use the experimental pressure signal,
obtained from piezo-electric transducers, the crank angle
position, obtained from optical encoders, and occasionally,
the injector needle lift, obtained from displacement sensors,
as input data. The pressure signal is then subjected to a
processing procedure consisting of cycle-averaging, filter-
ing, and referring to absolute pressure and crank-angle val-
ues. The obtained pressure function, together with the
cylinder volume one, which considers deformations caused
by inertia and pressure forces, are used to solve the instan-
*
Corresponding author. Tel.: +34 926 295 431; fax: +34 926 295 361.
E-mail address: Magin.Lapuerta@uclm.es (M. Lapuerta).
chamber with a state equation. Finally, after calculating
the thermodynamic properties of the gas and estimating
the heat transfer, the heat release law (time evolution of
heat release fraction, HRF) is solved with the first principle
of thermodynamics. This general procedure is shown in the
upper part of Fig. 1 for the particular case of the diagnostic
model used in the present work. In this case, the procedure
is repeated for each instant during the compression and
expansion strokes, some results from the previous step
being used for the present one.
Although the energy equation permits different
approaches such as those proposed in references [1–4],
the use of the ideal gas state equation is very common.
Both equations are significantly affected by the instanta-
neous gas composition, which depends on the fuel injection
rate, the exhaust gas recirculation rate and the fuel
composition.
Among the great number of uncertainties associated
with these methods [5,6], the use of the ideal gas state equa-

1359-4311/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.applthermaleng.2006.01.001
 M. Lapuerta et al. / Applied Thermal Engineering 26 (2006) 1492–1499 1493

Nomenclature

a coefficient of the state equations Subscripts

b coefficient of the state equations a air
fw function of the acentric factor b stoichiometric products
h enthalpy bb blow-by
m mass c critical
p pressure c released during combustion
Q heat fg gaseous fuel
R gas constant fl liquid fuel
T temperature inj injection
v specific volume r reduced
V volume w transferred to the walls
X mole fraction
Y mass fraction Superscripts
w Pitzer’s acentric factor 0 generalized
Z compressibility coefficient 1 deviations with respect to generalized

Fig. 1. Procedure for the combustion diagnostic in a Diesel engine and the selection of state equation.

tion should not be neglected. As some authors have already
reported [7,8], the selection of an appropriate state equa-
tion is essential for accurately solving the thermal and calo-
ric variables, and consequently for an accurate diagnostic
method, and it is even more important if any elucidation
about highly temperature dependant phenomena (heat
radiation, nitric oxides or soot formation mechanisms,
etc.) is pretended.
The deviations of the gas behaviour with respect to that
of an ideal gas are mainly due to the proximity of the ther-
modynamic conditions to those of saturation of some com-
ponents, and to the acentric behaviour of other
components [9]. In fact, the Redlich–Kwong and Soave
equations have often been used in literature for calculating
the phase equilibrium of the diesel fuel injected into the
combustion chamber [10–12].
1494 M. Lapuerta et al. / Applied Thermal Engineering 26 (2006) 1492–1499

The objective of this work is to quantify the errors asso-
ciated with the use of the ideal gas state equation and the
selection of the most appropriate one. With this purpose,
an additional procedure was integrated in the diagnostic
model, as sketched in the lower part of Fig. 1. The instan-
taneous computation of the reduced thermodynamic vari-
ables and the acentric factor permits to calculate the
compressibility factor through the generalized correlations
proposed by Lee and Kesler and based on the three-param-
eter corresponding states principle [13], and to compare it
with that provided by the state equation used in the model,
in order to select the most appropriate one by minimizing
errors.
2. Thermodynamic diagnostic model
Although the first principle is solved while intake and
exhaust valves remain closed, the combustion chamber is
an open system, due to fuel injection and blow-by. The
enclosed gas is a mixture of three components: gaseous fuel
(fg), air (a) and burnt products under stoichiometric condi-
tions (b). As diesel combustion is lean, the excess of air
mixes with combustion products during and after combus-
tion, but is not consumed [4]. This conception of the gas
mixture permits to instantaneously identify the gas compo-
sition and to estimate the thermodynamic properties of the
gas, as an average of those of the considered components.
Arrows numbers in Fig. 1 indicate the following
equations:
in the p–V diagram. For the other equations, further
corrections were made to improve predictions for acen-
tric hydrocarbons, as recommended in literature [9]. The
use of the latter equations permitted to evaluate the
effect of such acentricity or molecular nonsphericity,
which in the case of the considered fuel is not negligible.
2. Specific enthalpy correlations with temperature for the
three considered components and for the gas mixture.
The diesel fuel used for the computations is a commer-
cial automotive one supplied by Repsol-YPF, attaining
the present European standards (EN-590), with a sum-
marized formula C15.3H27.3. Its chemical composition
is also summarized in Table 2, and its specific enthalpy
was obtained by adding to the standard formation
enthalpy the integral of the specific heat function at con-
stant pressure, whose correlation coefficients were esti-
mated as an average of those of its components [3].Air
is considered as dry standard air. Finally, no fix compo-
sition can be taken for the stoichiometric products, due
to the dependence of dissociation with temperature and
pressure. From the resulting compositions of a 12 spe-
cies equilibrium model (N2, O2, CO2, H2O, CO, H2,
NO, OH, N, H, O, Ar) at different equilibrium temper-
atures and pressures, a single correlation with tempera-
ture was proposed for stoichiometric products.
However, the effect of pressure was not considered in
the correlations for this component, because such effect
is only significant at very high temperature, probably
above the range in which the mean cylinder temperature

1. State equation. Four state equations have been tested Table 2

(Table 1) apart from the ideal gas one. All of them are Chemical analysis of the used fuel
cubic, because the combustion chamber conditions are Ultimate analysis C 87
very similar to the critical conditions of the fuel. Recom- (% m/m) H 13
mended expressions for parameters a and b, as a func- Proximate analysis Saturates Paraffinics 32
tion of critical pressure and temperature, are used [9]. (% m/m) Naphtenics 33
Those of Van der Waals and Redlich Kwong equations Aromatics Mono-aromatics Benzenes 15
were obtained assuming that the critical isothermal Indanes 10
Diaromatics 10
curve has null slope and an inflexion in the critical point

Table 1
State equations
Equation Formula a b
2
27R T 2c
Van der Waals RT
p ¼ vb  va2 a¼ 64pc b ¼ RT
8p
c
c

0:42748R2 T 2:5
Redlich–Kwong RT
p ¼ vb a
 ðv2 þbvÞT 0:5 a¼ pc
c
b ¼ 0:08664RT
p
c
c

0:42748R2 T 2c 2
Soave RT
p ¼ vb a
 v2 þbv a¼ pc ½1 þ fwð1  T 0:5
r Þ b ¼ 0:08664RT
p
c
c

fw = 0.48 + 1.574w  0.176w2

0:45724R2 T 2c 2
Peng–Robinson RT
p ¼ vb a
 v2 þ2bvb2 a¼ pc ½1 þ fwð1  T 0:5
r Þ b ¼ 0:0778RT
p
c
c

2
fw = 0.37464 + 1.54226w  0.2699w
 M. Lapuerta et al. / Applied Thermal Engineering 26 (2006) 1492–1499
varies. Fig. 2 shows the specific heat at constant pressure
and the specific enthalpy for each of the three compo-
nents as a function of temperature and pressure. The
obtained correlations for the specific enthalpy of these
components are
ha ðJ=kgÞ ¼ 4193697:9  6:9466T 1:5 þ 2809:88T
 134454:16T 0:5 þ 917124:39 ln T þ 8349707:14T 0:5
hfg ðJ=kgÞ ¼ 1075458:24  242:96T þ 3:275T 2
 1:375  103 T 3 þ 2:348  107 T 4
hb ðJ=kgÞ ¼ 3314415 þ 1508T  0:30951T 2 þ 10:47  105 T 3
These correlations were used independently of the se-
lected state equation. This is justified because the ther-
modynamic effect of pressure (or volume) on enthalpy
is also negligible in the range of interest, as can be
proved if the enthalpy departures are calculated [7,8].
Finally, the enthalpy of the gas mixture (identified with
no subscript) is
h ¼ ha Y a þ hfg Y fg þ hb Y b
3. First principle of thermodynamics for open systems. The
formulation proposed in the present model is explained
in Ref. [4]. However, in order to avoid the presence of
internal energy (whose calculation from enthalpy
requires the use of the state equation) the following form
of the equation was preferred:
dQc ¼ mdh  V dp þ dQw
 
X fg pV pV
 hfl ðT inj Þ  hfg þ dmfg þ dmbb
mfg m used for calculating this instantaneous composition can
Using the Lee–Kesler departure function [13], a correla-
tion for the enthalpy of the injected liquid fuel as a linear
function of the temperature at the injector nozzle, was
obtained:
hfl ðT inj Þ ¼ 1; 852; 564 þ 2195T inj
Fig. 2. Specific enthalpy of the three considered components.
1495
ð1aÞ
Fig. 3. Gas constant of the burnt products.
ð1bÞ
4. Determination of the instantaneous gas composition.
The instantaneous values of gas composition, quantified
by the mass fractions of the three considered compo-
nents (Ya, Yfg, Yb), are modified along the injection
and combustion processes, as the calculated heat release
is supposed to be proportional to the burnt fuel mass.
The residual gas fraction in the cylinder after the
exhaust closure, the exhaust gas recirculation, the
short-circuited fresh mass and the blow-by are other
affecting parameters. Detailed description of the method
ð2aÞ
be found in Ref. [4].
5. Determination of averaged gas constant. After the gas
composition has been updated, the new constant of
the gas mixture is obtained as
ð2bÞ R ¼ Ra Y a þ Rfg Y fg þ Rb Y b ð3Þ
where Ra = 287 J/kg K, and from the considered refer-
ence fuel, the following values were obtained for the
other components constants: Rfg = 40.17 J/kg K; Rb =
285.9 J/kg K. The latter was again taken as constant de-
spite the variations with pressure and temperature
occurring at temperatures above 1800 K (see Fig. 3).
3. Evaluation of the thermodynamic behaviour of the gas
The thermodynamic behaviour of the gas was evaluated
by means of the procedure shown in the lower part of
Fig. 1. In order to avoid the use of addition rules such as
those of Barlett or Amagat [14] the mixture of gaseous
components was assumed to behave as a pure gas (Kay
rule) and thus, critical and reduced variables, as well as
acentric and compressibility factors, were calculated for
the mixture. The numbers on the arrows indicate the fol-
lowing operations:
1496 M. Lapuerta et al. / Applied Thermal Engineering 26 (2006) 1492–1499

Table 3 component, as none of them is pure. For the diesel fuel

Critical parameters and acentric factor for each component the average was made using mean values corresponding
Tc (K) pc (bar) w to the types of hydrocarbons shown in Table 2, with car-
Air 132.16 36.8 0.036 bon chains of around 15 atoms.
Diesel fuel 700.23 22.56 0.53 2. Determination of the Pitzer’s acentric factor of the com-
Stoichiometric products 217.1 63.4 0.1 ponents and of the gas mixture, from the updated com-
position. The acentric factor is not negligible in the case
Table 4
Engine characteristics
Engine Nissan YD22
Type DI-turbocharged-intercooled
Bore/stroke 86.5/94.0 mm
Compression ratio 18:1
Rated power 85 kW at 4000 rpm
Rated torque 237 N m at 2000 rpm

Table 5
Engine operating conditions
Operation mode Engine speed (rpm) Torque (N m)
A 1526 46
B 1743 77
C 1853 110
AFL 1526 205
BFL 1743 225
Fig. 5. Deviations of the compressibility factor along the engine cycle for
CFL 1853 230
different engine operation modes.

1. Determination of the gas mixture critical parameters

(actually pseudocritical parameters), from the updated
1.03 B Full load Lee Kesler
composition. Mole fraction averaging is recommended
Van der Waals Soave
for this determination [13]
Compressibility factor (Z)

1.025
Peng Robinson
T c ¼ X a T ca þ X fg T cfg þ X b T cb ð4aÞ 1.02

pc ¼ X a pca þ X fg pcfg þ X b pcb ð4bÞ 1.015

where subscripts ‘‘ca’’, ‘‘cfg’’ and ‘‘cb’’ correspond to 1.01

Redlich Kwong
the combination of ‘‘c’’, denoting critical, and the sub- 1.005
Ideal gas
script denoting the gaseous component. The same aver-
aging was previously used for each particular 1

0.995
-100 -80 -60 -40 -20 0 20 40 60 80 100
Crankangle

1.02 B Low load Lee Kesler

Soave
Compressibility factor (Z)

Van der Waals

1.015 Peng Robinson

1.01

1.005 Redlich Kwong

Ideal gas
1

0.995
-100 -80 -60 -40 -20 0 20 40 60 80 100
Crankangle

Fig. 6. Evolution of the compressibility factor obtained from Lee–Kesler

Fig. 4. Generalized compressibility factor along the engine cycle for correlations and from different state equations (Mode BFL above and
different engine operation modes. Mode B below).
 M. Lapuerta et al. / Applied Thermal Engineering 26 (2006) 1492–1499 1497

of long-chain hydrocarbons such as those of a diesel These correlations were derived from a modification of
fuel. Again, mole fraction averaging is recommended the Benedict–Webb–Rubin state equation, with experi-
for each component and for the gas mixture [14] mentally fitted constants, and is widely recognized as
one of the most accurate methods for simulating the ther-
w ¼ X a wa þ X fg wfg þ X b wb ð5Þ
modynamic behaviour of hydrocarbon-containing sys-
Table 3 shows the critical parameters and acentric factor tems. As the reduced pressure decreases or the reduced
of each component. temperature increases Z0 tends to unity and Z1 to zero,
3. Determination of the reduced pressure and temperature and thus the effect of acentricity becomes less significant.
of the gas mixture
T p Finally, comparisons were made between the compress-
Tr ¼ ; pr ¼ ð6Þ ibility factors of the gas mixture obtained from Eq. (7) and
Tc pc
from the state equations of Table 1, along the engine cycle.
4. The compressibility factor is obtained for the gas mix- From this comparison, the best state equation was selected,
ture as a function of the reduced thermodynamic vari- and used for comparisons of the diagnostic results with
ables and the acentric factor those obtained with the ideal gas state equation.
Z ¼ Z 0 ðT r ; pr Þ þ wZ 1 ðT r ; pr Þ ð7Þ
4. Experimental work
0 1
where Z and Z were obtained from the generalized
correlations proposed by Lee and Kesler based on the As an example of application of the proposed method,
three-parameter corresponding states principle [13]. the results of the combustion process diagnostic of a turbo-

B
2000 FL (Ideal) B
B (Ideal)
FL (Soave)
1800
In cylinder temperature (°C)

1600
B
1400 B (Soave) (Soave)

1200 B
(Ideal)
1000
B
FL (Ideal)
800 B
FL (Soave)
600

400
-100 -80 -60 -40 -20 0 20 40 60 80 100
Crankangle

35

30
Temperature difference (°C)

25 B
FL (Ideal-Soave)

20

15
B
(Ideal-Soave)
10

0
-100 -80 -60 -40 -20 0 20 40 60 80 100
Crankangle

Fig. 7. Evolution of mean cylinder temperature obtained from ideal state equation and from Soave equation (above) and differences between them
(below).
1498 M. Lapuerta et al. / Applied Thermal Engineering 26 (2006) 1492–1499

charged 0.55 l/cylinder direct injection Diesel engine, sup-
plied by Nissan (see Table 4), similar to those commonly
used in European passenger cars, were used as input. The
engine cylinder was instrumented with a water-cooled pie-
zoelectric pressure transducer Kistler 6061B and the injec-
tor needle was equipped with a displacement sensor.
This engine was tested in six different operating condi-
tions (see Table 5). Three of them were selected among
the collection of steady stages which reproduce the
sequence of operating conditions that the vehicles equipped
with this type of engines must follow during the transient
cycle established in the European Emission Directive 70/
220, amendment 2001/C 240 E/01. These modes constitute
more than 30% in time of the engine typical operation, and
are typically selected for combustion and emissions studies
under steady conditions. The other three modes are the
full-load modes corresponding to the same engine speeds.
Although the latter are no so usual during vehicle opera-
tion, they provide extreme pressure, temperature and fuel
concentration conditions, which is helpful to study the
range of applicability of the state equations.
5. Results and discussion
The evolution of the compressibility factor along the
engine cycle was firstly studied for different engine modes
by plotting the trajectories of the thermodynamic reduced
variables on graphics with constant compressibility factor
curves in the background. As the acentric factor is modified
with time in every case, two different plots were needed to
separate the generalized compressibility factor (Fig. 4)
from the deviations due to acentricity (Fig. 5). These fig-
ures show that the errors in the calculation of the gas tem-
perature can reach values higher than 2%, and that the
effect of the acentricity could even enhance such errors in
case that the fuel concentrations were significant.
This information is quantified for the cases of Mode B
and Mode BFL, as an example, in Fig. 6, where the com-
pressibility factor was obtained along the engine crank-
angle from the Lee–Kesler correlations, together with Eq.
(7), and from the different state equations. As it can be
observed, all the tested cubic equations improved notice-
ably their predictions with respect to the ideal gas equation,

1800

1600

1400 B
FL (Ideal)
1200 B
Heat Released (J)

FL (Soave)
1000
B (Ideal)
800

600 B
(Soave)
400

200

-200
-100 -80 -60 -40 -20 0 20 40 60 80 100
Crankangle

40

35
Heat Release difference (J)

30
B
FL (Ideal-Soave)
25

20 B
(Ideal-Soave)
15

10

0
-100 -80 -60 -40 -20 0 20 40 60 80 100
Crankangle

Fig. 8. Evolution of the heat release obtained from ideal state equation and from Soave equation (above) and differences between them (below).
 M. Lapuerta et al. / Applied Thermal Engineering 26 (2006) 1492–1499
but such improvements were even more significant in the
case of the acentric equations. This comparison permitted
to select Soave equation as the most appropriate one.
Finally, this equation was incorporated in the diagnostic
model, which permitted to quantify the differences between
the resulting mean temperature and heat release obtained
with this equation and with the ideal gas state equation
(Figs. 7 and 8). Prior to the analysis of such differences,
it can be noticed that the heat release rate and the temper-
ature peak are higher at full load, as expected. However,
compression temperature at partial load is higher than that
at full load, due to the increased exhaust gas recirculation.
As observed in the figures, differences in mean tempera-
ture are very small if compared with absolute values (max-
imum differences from 20 to 34 °C out of 1600 °C
variations, which corresponds to deviations between 1.3%
and 2.1%) and heat release (maximum differences from 14
to 38 J, which corresponds to deviations between 1.8%
and 2.1%). In any case, overestimations of the gas temper-
ature and of the initial heat release rate are achieved if the
ideal gas state equation is used.
However, in the case of the cylinder temperature, such dif-
ferences, occurring very close to the temperature peaks, may
provoke important errors in the estimation of heat radiation,
nitric oxide formation and soot formation, because these are
highly temperature-dependent phenomena.
6. Conclusion
The use of ideal gas state equation is generalized in com-
bustion diagnostic procedures aiming to obtain informa-
tion about the cylinder gas temperature and the heat
release rate from the experimentally obtained cylinder pres-
sure signal. However, other state equations provide
improvements in the temperature estimation, as well as in
the heat release estimation through the first principle of
thermodynamics. Detailed instantaneous estimation of
the gas mixture thermodynamic properties is needed for
comparing the state equations behaviour. Among the
tested state equations, the cubic and acentric ones showed
the best performance because the combustion chamber
conditions are very similar to the critical conditions of
the fuel and because of the acentricity of the fuel is high.
Such improvements are even more significant at high load,
as the fuel concentration is higher. Taking the compress-
ibility factor obtained from the generalized correlations
proposed by Lee and Kesler as reference, the Soave equa-
tion was proved to provide the best predictions. When
the obtained mean temperature and heat release were com-
pared with those obtained with ideal gas state equation,
small relative differences were obtained. However, such dif-
ferences may become important in case that the diagnostic
1499
results are used to estimate or simulate highly temperature-
dependent phenomena.
Acknowledgements
The authors wish to acknowledge the Spanish Ministry
of Science and Technology for the financial support (Pro-
ject DIMCI, ref: DPI2001-2704-C02), the Spanish Ministry
of Education, Culture and Sports, for the postdoctoral
sponsorship of John R. Agudelo at the University of Cas-
tilla–La Mancha, Repsol-YPF for the supply and chemical
analysis of the diesel fuel, and Marı́a Rodrı́guez de la Ru-
bia for her help.
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