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Thermodynamic requirements for maximum internal combustion engine

cycle efficiency. Part 1: Optimal combustion strategy

Article  in  International Journal of Engine Research · December 2008

DOI: 10.1243/14680874JER01508

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 International Journal of Engine Research
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Thermodynamic requirements for maximum internal combustion engine cycle efficiency. Part 1:
Optimal combustion strategy
K-Y Teh, S L Miller and C F Edwards
International Journal of Engine Research 2008 9: 449
DOI: 10.1243/14680874JER01508

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 449

Thermodynamic requirements for maximum internal

combustion engine cycle efficiency.
Part 1: optimal combustion strategy
K-Y Teh*, S L Miller, and C F Edwards
Department of Mechanical Engineering, Stanford University, Stanford, California, USA

The manuscript was accepted after revision for publication on 26 July 2008.

DOI: 10.1243/14680874JER01508

Abstract: This is the first of a two-part study that examines, from the exergy management
standpoint, the fundamental thermodynamic requirements for maximizing internal combus-
tion (IC) engine cycle efficiency. The optimal cycle is shown to comprise three distinct engine
architectural elements – reactant preparation, combustion, and work extraction from the
products – each of which can be analysed separately. This study shows, based on dynamical
system optimization, that it is the equilibrium thermodynamics (specifically, the constant-
internal energy–volume (UV) product state at the end of combustion) and not chemical kinetics
(i.e. reactions taking place during combustion) that ultimately dictates the amount of exergy
destroyed due to combustion. The strategy for minimizing this destruction term reduces to
carrying out reactions at the highest possible internal energy state – following what may be
called the ‘extreme state’ principle – so as to minimize the corresponding constant-UV entropy
change from reactants to equilibrium products. The extreme state principle remains unaltered
when system inhomogeneity (from fuel vaporization and mixing with air) and heat loss are
accounted for. Based on this optimal combustion strategy, the companion paper examines the
remaining elements of the engine cycle (reactant preparation and work extraction) so as to
improve overall cycle efficiency.

Keywords: combustion, entropy generation, exergy destruction, internal combustion engine

efficiency, optimal engine cycle, thermodynamics

1 INTRODUCTION engine efficiencies and what is possible given the

Engines convert energy in a resource into work. In
the case of an internal combustion (IC) engine, the
fuel–oxidizer mixture (fuel being the chemical energy
resource) that undergoes chemical reactions also
functions as the working fluid that produces expan-
sion work. IC engines dominate the road transporta-
tion sector, which accounted for 1.66103 million
tonnes of oil equivalent – or 21 per cent – of global
energy consumption (end-use) in 2004 [1]. The
attendant CO2 emission was 4.66103 million tonnes,
or 17 per cent of CO2 emissions worldwide [2]. Yet
there exists a sizable gap between state-of-the-art IC
*Corresponding author: Sandia National Laboratories, Combus-
tion Research Facility, PO Box 969, MS9052, Livermore, CA
94551-0969, USA. email: kteh@sandia.gov
laws of thermodynamics. Furthermore, an important
source of the inefficiency is still not well understood.
1.1 Reactive engine efficiency
The absolute maximum work extractable from a
resource, set by the laws of thermodynamics, is
called the ‘resource exergy’. In order to achieve this
maximum-work limit it is required that the engine:
(a) processes the resource reversibly (e.g. when
converting reactants to products), and (b) interacts
with the environment via reversible transfers (e.g.
when bringing in oxygen from the environment to
oxidize the fuel). It follows that exergy is a function
of the thermodynamic state of the resource as well as
its environment.

JER01508 F IMechE 2008 Int. J. Engine Res. Vol. 9

450 K-Y Teh, S L Miller, and C F Edwards
For example, given some amount of fuel, the
corresponding fuel exergy (denoted X) is
X eration of the second law [3]. Therefore, it is not
X ~UzP0 V {T0 S{ mj,0 nj N
j per cent by this efficiency measure.) In contrast,
where U, V, S, and N refer to the internal energy,
volume, entropy, and moles of fuel respectively; P0,
T0, and mj,0 are the ambient pressure, temperature,
and chemical potential respectively for each species
j present in the environment; nj is the (signed)
stoichiometric coefficient for species j in converting
one mole of fuel to environmental products
X next section – it is worth noting the distinction
ðFuel speciesÞ? nj ðenvironmental species jÞ
j latter system, supplied with energy Q in the form of
In addition to the fuel exergy, other maximum-
work limits can be defined based on the thermo-
dynamic constraints imposed upon the engine to
which the fuel is supplied. For instance, part of IC
engine operation (between intake valve closing and
exhaust valve opening) is usually modelled as an
adiabatic process for a closed system. Under these
conditions, the second law dictates that the combus-
tion product final entropy must be greater than, or at
best equal to, the initial entropy of the reactants in
the system. Therefore, the corresponding maximum
engine work output is the difference in internal
energy U between reactants and products at the
same entropy S. As regards notation, the operator Dr
will be used here to refer to state change from
reactants (subscripted ‘R’) to products (‘P’). In the
case just described, if the product gas mixture is also
taken to be at the same volume V as the initial
reactant mixture, the maximum-work limit will then
be denoted
jDr U jS,V ~jUP ðS, V Þ{UR ðS, V Þj
As another example, fuel cells are often modelled as
isothermal, isobaric flowing systems, i.e. operating
at some fixed temperature T and pressure P. The
maximum work that can be extracted from
the reactants supplied to such a system equals the
Gibbs’ free energy difference |DrG|T,P between the
reactants and products at T and P.
Table 1 lists these maximum-work limits (some-
times called ‘second-law limits’) for several fuels.
The limits are comparable with the respective fuel
lower heating values (LHVs, equal to |DrH|T,P at
standard-state T 5 25 uC, P 5 1 atm). The theoretical
limits on the efficiency of engines supplied with
these fuels, measured as work produced per unit
LHV (also called the ‘thermal’ or ‘fuel-conversion
efficiency’), range between 89 and 107 per cent. (The
Int. J. Engine Res. Vol. 9
choice of LHV as the basis for defining fuel
conversion efficiency is empirical, without consid-
impossible for maximum-work limits to exceed 100
today’s IC engines have peak brake thermal efficien-
cies ranging from low 30s to mid 40s [3]. Clearly,
there is substantial room for efficiency improvement
and thus the potential for significant reductions in
fuel resource consumption and CO2 emissions.
Before reviewing past thermodynamic analyses of
the causes for this efficiency gap – the subject of the
between a reactive engine and a heat engine. For the
heat transfer from a thermal resource at some high
temperature T . T0, only a fraction of the energy can
be converted to work W, such that


T0
Max W ~ 1{ Q
T
yielding the heat engine Carnot efficiency, 1 2 T0/T,
which is a function of the thermodynamic state for
the thermal resource (temperature T) and that of the
surroundings (temperature T0). The maximum-work
limits listed in Table 1 are, in a similar manner,
functions of the thermodynamic state for the
chemical resource, i.e. the fuel, and that of the
surroundings. It is important to recognize that the
peak temperature that a combustion engine reaches
during operation does not figure in the maximum-
work limit calculations, since it is not a heat engine.
1.2 Exergy analyses of IC engines
Exergy is a useful concept for evaluating the
performance of various energy systems and, through
its balance equation, identifying and quantifying
inefficiencies in the underlying thermodynamic
processes [4]. From this perspective, the challenge
of building an efficient energy system becomes a
matter of managing the resource exergy supplied to
it to minimize exergy losses and, in the case of an
engine, maximize exergy outflow in the form of
work. The present paper offers, from this exergy
management viewpoint, a discussion as to what
comprises the optimal IC engine thermodynamic
cycle, i.e. one that maximizes the engine efficiency.
Exergy analysis (sometimes referred to as ‘second-
law analysis’) of IC engines has been the subject of
JER01508 F IMechE 2008
 Thermodynamic requirements for maximum IC engine cycle efficiency. Part 1 451

Table 1 The maximum-work limits and lower heating values for some fuels (in MJ/kg fuel)
{
*
Fuel species Chemical formula X (fuel exergy) |DrU|S,V |DrG|T,P |DrH|T,P (LHV)
Hydrogen H2 117.2 107.0 111.4 120.0
Methane CH4 51.9 49.8 49.8 50.0
Ethanol C2H5OH 29.6 28.4 28.4 27.7
Propane C3H8 48.8 47.0 47.1 46.3
Isooctane C8H18 47.5 45.8 45.9 44.7

*All species are taken as ideal gases. Reactions are with stoichiometric air at 25 uC, 1 atm.
{
The environment is taken as 25 uC, 1 atm, 363 ppm CO2, 2 per cent H2O, 20.5 per cent O2, balance N2.

many studies; see, for example, review articles [5]
and [6]. These studies consistently show that four
terms dominate the exergy balance as applied to
the engine cylinder (excluding subsystems for
compounding): (a) exergy destruction due to
combustion; (b) exergy transfer associated with
heat loss; (c) exergy in the exhaust of the combus-
tion products; (d) work due to gas expansion. By
contrast, exergy destruction terms due to mixing
and pumping losses are typically one or two orders
of magnitude smaller. Table 2 shows representative
values for the net transfer and destruction terms
over one engine cycle taken from studies by Caton
[7] and Primus et al. [8]. These studies indicate that
maximizing the expansion work – and thus engine
efficiency – requires careful management of the
remaining three dominant exergy destruction and
transfer terms.
This observation is not new, since the various
elements of the exergy management strategy have
been discussed in the past, albeit at varying levels of
detail and understanding. Several studies have
provided insights into the concepts of turbocharging
and compounding (to recover a portion of the
Table 2 Representative results from exergy analyses
of spark-ignition (SI) and compression-
ignition (CI) engines in the literature [7, 8]
SI engine* CI engine{
Exergy balance terms (% fuel exergy) (% fuel exergy)
Destruction due to 20.6 15.9
combustion
Net transfers with:
heat loss 23.0 21.4
exhaust 24.7 20.4
expansion
{
work 29.7 39.1
Balance 2.0 3.2
*Based on a V-8 engine operating at part-load (1400 r/min, 27 kW)
[7].
{
Based on a naturally aspirated, direct-injection CI engine at
2100 r/min, 185 kW [8].
{
For the SI engine, the balance includes destruction due to inlet
mixing and exergy of unburned fuel (distinct from the product
exhaust exergy term). For the CI engine, it includes destruction
due to intake and exhaust valve throttling.
exhaust sensible energy for use) as well as engine
insulation (to reduce heat transfer losses), by placing
these thermal strategies in the context of reducing
the respective exergy transfer terms [8–10]. For
instance, the effects of insulation – both direct
(reduced exergy outflow with heat transfer) and
indirect (higher in-cylinder temperature, leading to
increased compression work, throttling losses, and
exhaust exergy) – have been described in detail by
Primus et al. [8].
By comparison, exergy destruction associated with
combustion – a chemical transformation process – is
less well understood. (It has been said that the term
‘remains the most obscure and difficult availability
destruction to cope with’ [6].) Some trends with this
destruction term have been noted previously. For
instance, it decreases with increasing adiabatic
flame temperature (brought about by compressing
the reactant, heating it, or increasing its equivalence
ratio towards stoichiometric) for combustion at
constant pressure as well as at constant volume
[11–13]. On the other hand, many important para-
meters of the combustion process, including its
duration, temporal profile, and ignition timing, were
found to have only a slight impact on the amount of
exergy destroyed [14–16]. The present paper pro-
vides a thermodynamic explanation that unifies
these seemingly disparate results. Its implications
on the exergy management approach to raising IC
engine efficiency will also be discussed here and in
the companion paper [17].
1.3 Paper outline
In the next section, an explanation is given of
terms that contribute to the exergy balance equa-
tion as applied to IC engines, and the equation is
simplified for the case of an adiabatic, homoge-
neous engine model. This model isolates combus-
tion as the only mechanism for exergy destruction,
which is to be minimized. While the exact mathe-
matical treatment of this optimization problem is
presented elsewhere [18], its thermodynamic im-

JER01508 F IMechE 2008 Int. J. Engine Res. Vol. 9

452 K-Y Teh, S L Miller, and C F Edwards
plications on IC engine efficiency are elaborated in
section 3 of this paper. Sections 4 and 5 clarify the
effects on the optimal (i.e. minimum exergy
destruction) strategy when the stipulations that
the system be homogeneous and adiabatic are
lifted.
In Part II of this study [17], a separate set of
thermodynamic requirements for optimal expansion
(i.e. maximum work extraction) is discussed and
contrasted with the conditions imposed by the optimal
combustion process. Given these twin sets of pre-
requisites, the companion paper then examines
several resource preparation strategies – reactant
compression, dilution, heating, and cooling – so
that the ensuing reaction (combustion) and work
extraction processes can be carried out in an optimal
fashion.
2 THE EXERGY BALANCE AND ITS
MANAGEMENT
Consider as a thermodynamic system the in-cylinder
fuel–air mixture during the closed portion of IC
engine operation between intake valve closing and
exhaust valve opening. A balance equation describ-
ing the evolution of exergy of the working fluid may
be written as
ðf ðf
Xf {Xi ~ dX ~ dXin {dXout {dXdest ð1Þ
i i
where Xi is the initial exergy of the system, dX is its
differential exergy change, the dX terms are differ-
ential amounts of exergy transferred in or out, or
destroyed by irreversible (i.e. entropy-generating)
processes, and Xf is the final working fluid exergy
that remains at the end.
Equation (1) indicates how the engine expansion
work output – a component of the exergy outflow
term $dXout – is affected by other aspects of its
operation. In this closed-system formulation, the
remainder of the outflow term can be entirely
ascribed to heat loss to the cooling jacket, while
the exergy associated with engine exhaust is sepa-
rately accounted for by the final exergy term Xf.
Working fluid compression constitutes an exergy
investment, given by the inflow term $dXin, whereas
exergy destruction, given by the term $dXdest and
largely due to combustion-generated entropy, can
never be recovered. These aspects of IC engine
operation dominate the exergy balance equation (1),
Int. J. Engine Res. Vol. 9
as typified by the results shown in Table 2. The
balance equation makes evident the fact that these
exergy terms are intimately related. For instance, in
the engine insulation study discussed in reference
[8], not all the exergy retained by reducing engine
heat loss is extracted in the form of work, i.e. the
total exergy outflow $dXout is not fixed. Instead, a
substantial fraction is left in the exhaust stream
(indicated by high Xf), recoverable only via com-
pounding.
Now consider a homogeneous, adiabatic IC engine
model that takes into account all significant effects
except for heat loss and gas mixing. Excluding heat
transfer and other spatial inhomogeneities isolates
combustion as the sole source of exergy destruction
and simplifies the model for mathematical analysis.
(The effects of reactant mixing and heat transfer on
the exergy destruction minimization strategy are
examined later in sections 4 and 5.) Under these
stipulations, boundary work is the only permissible
mode of exergy transfer into or out of the system, so
that the net transfer is
dXin {dXout ~{ðP{P0 Þ dV ~dUzP0 dV ð2Þ
where the first law for a closed, adiabatic system
dU 5 2P dV has been incorporated in the expres-
sion.
Heat and matter transfers are absent in this model,
as are the associated entropy flows. Hence, any
entropy change within the system can be attributed
to the entropy generated during combustion, and
thereby the exergy destroyed (scaled by ambient
temperature T0)
dXdest X mj
~dSgen ~dS~{ dNj ð3Þ
T0 j
T
Based on the first equality, often attributed to Gouy
and Stodola, the terms ‘exergy destruction’ and
‘entropy generation’ will be used interchangeably
for the remainder of this paper. The last equality
relates the system entropy increase to changes in its
chemical composition due to combustion. It comes
from combining the first law with the Gibbs
equation. Equations (2) and (3) reduce the balance
equation (1) to
Xf {Xi ~ðUf {Ui ÞzP0 ðVf {Vi Þ{T0 ðSf {Si Þ ð4Þ
Various aspects of the exergy management strategy
revolving around this balance equation will be
JER01508 F IMechE 2008
 Thermodynamic requirements for maximum IC engine cycle efficiency. Part 1
discussed in the following sections and the compa-
nion paper.
3 STRATEGY FOR MINIMUM EXERGY
DESTRUCTION DUE TO COMBUSTION
As the review of past second-law analyses (section
1.2) indicates, exergy destruction due to combustion
remains a concept that is not well understood, even
though it accounts for as much as a quarter of the
fuel exergy supplied to an IC engine. In fact, it can be
shown that this destruction term is minimized (and
engine efficiency increased) by the strategy of
constant-UV equilibrium entropy minimization.
The reader is referred to reference [18] for a detailed
mathematical treatment of the subject, which is
based on the homogeneous, adiabatic IC engine
model introduced above and formulated as a
dynamical system optimal control problem.
The thermodynamics underlying the optimal
solution is presented in this section. The discussion
provides a framework for dealing with issues
associated with the homogeneity and adiabatic
assumptions – the implementation challenges as
well as opportunities with fuel–air mixing in the
former case, the problem of heat transfer losses in
the latter case – which are topics for the next two
sections.
3.1 Thermodynamics of the optimal solution
The optimal solution for minimum exergy destruc-
tion due to combustion in a piston engine can be
summarized as
(a) rapid compression of the reactant mixture when
cylinder pressure is below the corresponding
constant-UV equilibrium pressure (and while
chemical reactions proceed);
(b) rapid expansion of the products when cylinder
pressure exceeds its corresponding constant-UV
equilibrium value.
In thermodynamic terms, the optimal solution above
reduces to a strategy that minimizes the constant-
UV equilibrium entropy of the system of in-cylinder
gases.
This equilibrium corresponds to the combustion
product state in the limit of instantaneous (and
therefore constant volume), complete reaction. For a
more precise definition – crucial to understanding
the strategy outlined above – it is first noted that the
internal energy U, volume V, and chemical species
JER01508 F IMechE 2008
453
composition N (a vector of mole numbers) of a
closed, homogeneous system at any point in time
constitute a natural set of variables sufficient to
describe fully its thermodynamic state at that
instant. The corresponding constant-UV equili-
brium, denoted by the subscript ‘eq’, is then the
state that the system would have reached had it
undergone chemical reactions to completion while
being isolated with internal energy and volume fixed
at instantaneous values U, V, and with its atomic
composition unchanged. In other words – and this is
the pivotal and recurring concept in the present
discussion – the constant-UV equilibrium state is
always the attractor for the actual system at any
point in its thermodynamic state space (U, V, N), in
accordance with the second law.
The entropy function S(U, V, N) is used to quantify
this property for a closed system. The function is
maximized at the constant-UV equilibrium state
 
Seq U, V , N eq ¢SðU, V , N 0 Þ
for the set {N9} of all possible mixture compositions
with the same atomic composition, including the
actual, instantaneous composition of the system
N [ {N9}. Applying the maximum-entropy principle to
equation (3), which is restated here on a time-rate
basis, yields the inequality displayed below.
1 dXdest dSgen dS X mj
~ ~ ~{ fj ðU,V ,N Þ¢0 ð5Þ
T0 dt dt dt j
T
Here, fj 5 dNj/dt is the net production rate of species
j due to chemical reactions taking place in-cylinder.
For gas-phase (i.e. combustion) kinetics, these rates
are determined based on the mixture’s thermody-
namic state (U, V, N). (The equality holds only at
equilibrium, such that Smj,eq fj (U, V, Neq) 5 0, which
reduces Gibbs’ equation to Teq dSeq 5 dUeq + Peq
dVeq.)
For a closed, adiabatic system, equation (5) shows
that its rate of entropy generation due to combustion
at every point in time is dictated solely by its
thermodynamic state at that instant. The equation
provides no indication as to how entropy generated
within the system can be minimized via boundary
work, which is the only permissible mode of energy
interaction. This is the rationale for introducing the
constant-UV equilibrium concept: a strategy invol-
ving compression and expansion work (namely, the
optimal solution summarized above) can be devised
to minimize the entropy of this equilibrium state.
More importantly, the exact same strategy would
Int. J. Engine Res. Vol. 9
454 K-Y Teh, S L Miller, and C F Edwards
also minimize entropy generation from the actual
thermodynamic system (i.e. the in-cylinder gas
mixture), since the system must satisfy the require-
ment of complete reaction – to avoid quenching or
incomplete combustion – and thus necessarily
approach equilibrium at the end of the engine cycle.
The optimal strategy can be explained by con-
sidering changes in the volume and internal energy
variables. For the actual adiabatic system, these
changes are related by the energy balance
dU 5 2P dV. It also means, by definition, that
variables Veq and Ueq for the corresponding con-
stant-UV equilibrium attractor would change by the
same amount. Therefore
dVeq ~dV
dUeq ~dU~{P dV ~{P dVeq
This means that Gibbs’ equation at equilibrium can
be written as
 
Teq dSeq ~dUeq zPeq dVeq ~ {PzPeq dV
Equation (7) makes evident the strategy for mini-
mizing entropy of the constant-UV equilibrium state
via boundary work.
1. Gas compression, dV , 0. Gas compression –
constituting a marginal investment in the form
of work (dV , 0, dU 5 2P dV . 0) – is optimal at
each instant when the system pressure is below
the corresponding constant-UV equilibrium pres-
sure, Peq 2 P . 0. The resulting change in equili-
Fig. 1 The equilibrium entropy minimization strategy for reducing exergy destruction due to
combustion. (a) Optimal U, S and corresponding U, Seq trajectories. (b) Trajectories near
chemical equilibrium
Int. J. Engine Res. Vol. 9
brium entropy would then be negative
{1
 
dSeq ~Teq Peq {P dV v0
2. Gas expansion, dV . 0. Gas expansion (work
extraction) is optimal at each instant when the
system pressure exceeds its constant-UV equili-
brium value, as that also leads to a decrease in
equilibrium entropy: dV . 0 and Peq 2 P , 0 imply
{1
 
dSeq ~Teq Peq {P dV v0
The strategy of equilibrium entropy minimization
is best depicted on the internal energy/entropy
diagram, as shown in Fig. 1. It is based on the
numerical example used in reference [18] for the
optimal combustion of a stoichiometric propane/air
ð6Þ mixture with 50 per cent exhaust gas recirculation
(EGR). (Appendix 2 includes additional comments
on the illustrative examples used in this paper.) The
figure includes the optimal U, S trajectory as well as
its constant-UV equilibrium counterpart, showing
that the thermodynamic state of the reacting gas is
ð7Þ
indeed being steered such that the constant-UV
equilibrium entropy is always decreasing.
These trajectories typify combustion of common
fuel–air mixtures. Since the combustion process is
exothermic, the mixture pressure would initially be
lower than its corresponding constant-UV equili-
brium value, Pi , Peq,i. This condition calls for gas
compression such that the equilibrium entropy
decreases. Chemical reactions are typically negligi-
ble during the initial reactant compression process,
but as the mixture temperature and pressure
JER01508 F IMechE 2008
 Thermodynamic requirements for maximum IC engine cycle efficiency. Part 1
increase, chemical kinetics accelerate until the
mixture autoignites. The optimal U, S trajectory –
process i–B̄ in Fig. 1(a) – reflects this; it starts off
largely isentropic while internal energy U increases,
but curves to the right as the reaction proceeds with
an attendant increase (i.e. generation) of entropy S.
Upon autoignition, the optimal trajectory shows
significant entropy generation with small internal
energy increase, which indicates that the reactants
are converted to products very rapidly in compar-
ison to the rate of compression.
The pressure difference Peq 2 P . 0 diminishes as
chemical reaction (and compression) proceeds, and
reaches zero at point B̄. This point is close to
chemical equilibrium, signifying that combustion is
near completion at this juncture (92 per cent
combustion efficiency). It should be noted that the
criterion P 5 Peq does not imply equilibrium has
been reached. (If a system is at equilibrium, then its
pressure P 5 Peq. The converse, however, need not
be true.) In fact, the in-cylinder pressure proceeds to
overshoot its equilibrium value by a small margin
past point B̄. Using the ideal gas model
   
SNj R
T SNj,eq R
Teq
PwPeq [ w ð8Þ
V Veq
where V 5 Veq. Given the complex nature of finite-rate,
detailed combustion chemistry, it is not inconceivable
for the actual gas composition and temperature to
differ from the constant-UV equilibrium values such
that, upon multiplication, (SNj)T exceeds (SNj,eq)Teq.
For example, SNj . SNj,eq may indicate excess radical
species yet to recombine to yield stable products at
equilibrium; T . Teq may be due to slow, endothermic
reactions (e.g. NO formation).
Following the optimal strategy, inequality (8) calls
for gas expansion such that the constant-UV equili-
brium entropy decreases. Since combustion is
effectively complete, entropy generation during
expansion is typically miniscule. This is illustrated
by process B̄–C̄9 and the corresponding equilibrium
U, Seq trajectory in Fig. 1. The calculation was
terminated at point C̄9, where the complete-reaction
criterion (97 per cent combustion efficiency) was
reached. After that point, a dashed line is appended
to indicate isentropic expansion of the combustion
products to the initial system volume (point C̄).
It should be emphasized that combustion and the
consequent entropy generation are accounted for
throughout process i–B̄–C̄9. (This includes the case
where combustion begins and approaches comple-
tion, all while the volume is still being reduced.)
JER01508 F IMechE 2008
455
Combustion kinetics affect the instantaneous mixture
composition, temperature, and thus pressure, which in
turn determine the optimal switching point, P 5 Peq at
B̄. Notwithstanding these effects of detailed kinetics,
the optimal solution means that it is the equilibrium
thermodynamics (specifically, the constant-UV pro-
duct states at the end of combustion) and not chemical
kinetics (i.e. reactions taking place during combustion)
that ultimately dictates the amount of exergy de-
stroyed. (This explains the very mild dependence of
the entropy generation term on various parameters of
the combustion process, as mentioned in the intro-
duction, i.e. section 1.2, references [14] to [16].) After
all – and to reiterate our main conclusion – the strategy
of minimizing entropy Seq for the constant-UV
equilibrium to which a closed system of reacting gases
is attracted will also, by virtue of the requirement for
complete reaction, minimize the actual entropy gen-
eration due to combustion of the gas mixture.
3.2 Compression ratio constraint
Figure 1 illustrates the well-known fact that a fuel–
air mixture cannot be compressed with no limit (or,
in equivalent terms, its internal energy cannot be
raised indefinitely) without combustion taking place,
which accounts for the fundamental constraint on
compression ratio of premixed/homogeneous-
charge, spark-ignition engines. At any rate, engine
geometry imposes a separate, practical constraint on
the minimum allowable clearance volume and it
defines the engine compression ratio. Nevertheless,
it is important to recognize that the approach for
minimizing entropy generation due to combustion is
unaltered even when this clearance volume con-
straint is included. After all, the requirement that the
product gases reach equilibrium at the end of the
engine operating cycle is unchanged. Hence, the
strategy of minimizing entropy Seq for the constant-
UV equilibrium attractor also remains valid.
As pointed out in the previous section, the initial
pressure Pi of common fuel–air mixtures is below
that of its constant-UV equilibrium counterpart Peq,i
since combustion is exothermic. Compression of the
fuel–air mixture then results in entropy reduction for
its corresponding constant-UV equilibrium state.
This compression strategy applies until the engine
compression ratio is reached.
It is reasonable to assume that Peq 2 P . 0 at this
phase of the optimal engine operating cycle. Had the
clearance volume constraint been absent, the equili-
brium attractor entropy minimization strategy would
have called for further gas compression (thus reverting
Int. J. Engine Res. Vol. 9
456 K-Y Teh, S L Miller, and C F Edwards
to the optimal solution presented in section 3.1).
Given the constraint, however, the strategy is to
maintain the gas volume (which, under adiabatic
conditions, implies fixed attractor entropy dSeq 5 0)
rather than expand the gas (which leads to attractor
entropy increase dSeq . 0). Chemical kinetics will
accelerate during this constant-volume phase, until
the in-cylinder pressure overshoots the corresponding
constant-UV equilibrium pressure, after which the
optimal strategy is, again, gas expansion.
To summarize, in a typical IC engine subject to a
compression ratio constraint, the optimal operating
cycle that minimizes the entropy generation due to
combustion is:
(a) rapid compression of the reactant mixture to
the minimum allowable volume set by the
engine compression ratio (while chemical reac-
tions proceed);
(b) maintenance of the clearance volume until the
cylinder pressure rises to its corresponding con-
stant-UV equilibrium value (due to combustion);
(c) rapid expansion of the products.
For example, Fig. 2 shows the U, S diagram for
optimal combustion of the same homogeneous
mixture considered previously (stoichiometric pro-
pane/air, 50 per cent EGR), albeit constrained by 13:1
compression ratio. (Without the compression ratio
constraint, the mixture would ignite upon compres-
sion near a volume ratio of 19:1; see Fig. 1.) Again, the
optimal U, S and equilibrium U, Seq trajectories illus-
trate the equilibrium entropy minimization strategy
during compression (process i–A in Fig. 2(a)) as well
as expansion (B–C9 in Fig. 2(b)). Point C9 lies close to
Fig. 2 The strategy of equilibrium entropy Seq minimization remains unaltered upon
consideration of the IC engine compression ratio constraint. (a) Optimal U, S and
corresponding U, Seq trajectories. (b) Trajectories near chemical equilibrium
Int. J. Engine Res. Vol. 9
chemical equilibrium, which signifies near-complete
reaction (98 per cent combustion efficiency). An
isentropic line (dashed) is appended to indicate
combustion product expansion to the initial system
volume (point C).
Not surprisingly, the reactant compression pro-
cess is largely isentropic as the fuel–air mixture does
not autoignite before compression to the clearance
volume (point A). Similarly, exergy destruction
during expansion of the combustion products is
also minuscule, since the optimality criterion for
expansion, P . Peq, is only satisfied when the system
is close to chemical equilibrium. As a result, entropy
generation during combustion at the clearance
volume dominates the exergy destruction term. In
other words, the optimal operating cycle for the
homogeneous, adiabatic IC engine model is approxi-
mately an ideal fuel–air cycle, consisting of the
following sequence of processes:
(a) isentropic compression of the reactant mixture
– with its chemical composition frozen – to the
engine clearance volume;
(b) constant-volume combustion, converting the
reactants into products at thermodynamic
equilibrium;
(c) isentropic expansion of the equilibrium product
mixture.
Depending on the assumption, the expansion may
end at some prescribed final volume (e.g. symmetric
expansion to the initial volume, akin to the Otto
cycle) or pressure (e.g. expansion to the atmospheric
or exhaust pressure, akin to the Atkinson cycle), with
JER01508 F IMechE 2008
 Thermodynamic requirements for maximum IC engine cycle efficiency. Part 1
corresponding implications on the maximum ex-
pansion work output from each cycle.
This is an important result that warrants amplifi-
cation. It means that at any given compression ratio,
piston engine efficiency is maximized when com-
bustion occurs at the minimum allowable volume.
This is a far stronger assertion than what is already
well known – that efficiency is highest for the
constant-volume combustion cycle as compared
with the constant- and limited-pressure cycles (also
known as the diesel and dual cycles) [3] – since the
optimal solution presented above is obtained upon
consideration of all possible engine operating cycles.
The optimization results presented above,
founded upon the equilibrium attractor entropy
minimization strategy given by equation (7), also
discount the notion that simultaneous work transfer
and chemical reactions could enhance the efficiency
of combustion engines. Instead, the chemical reac-
tions are ‘separable’ from the mechanical (compres-
sion and expansion) processes at optimality. Each of
the three processes enumerated in the optimal
sequence above correlates to one of three essential
elements of engine architecture: preparation, reac-
tion, and extraction of work from the energy
resource (i.e. the fuel) supplied to the engine. The
concept of separability allows each of these archi-
tectural elements to be analysed individually, while
ascribing the entropy generated over the entire
operating cycle to just the reaction stage of the cycle.
3.3 Exergy destruction due to constant-UV
combustion
The discussion thus far points to the equilibrium
thermodynamic states for products of combustion as
the most crucial element in the entropy generation
minimization scheme. In the case of an IC engine with
a compression ratio constraint, it is noted that the
magnitude of the entropy generation term is very
close to the entropy difference between the reactants
and its constant-UV equilibrium products at the same
clearance volume. This approximation reduces the
question of exergy destruction minimization from a
more challenging problem involving reaction kinetics
and other non-linear dynamics, to a substantially
simpler problem involving only the thermodynamics
of the reacting gas mixture at two points, i.e. its initial
reactant and final product states. The present section
analyses this thermodynamic problem.
Consider a thermodynamic system composed of
an unreacted (i.e. chemically frozen) fuel–air mixture
at the start of combustion, and fully reacted (i.e.
JER01508 F IMechE 2008
457
equilibrated) products at the end of the process. In
each case, the system thermodynamic properties are
fully defined by a fundamental relation of the form
U~U ðS, V , N Þ ð9Þ
In physical terms, this equation describes the
functional interdependence between the internal
energy U, entropy S, and volume V as the gas
mixture is manipulated thermally (heated or cooled)
or mechanically (compressed or expanded). In
differential terms, this functional dependence takes
the form of Gibbs’ equation
dU~T dS{P dV ð10Þ
in which the term Smj dNj associated with chemical
transformation does not appear. In the case of the
frozen reactants, this is because the mole number Nj
of each chemical species is fixed, so the change dNj
is always zero. (The system is said to be in restricted –
i.e. thermal and mechanical, but not chemical –
equilibrium.) In the case of the products, the sum
vanishes under the assumption of chemical equili-
brium. The fundamental relation (9) for U can
therefore be represented graphically as a two-
dimensional manifold of S and V.
For example, the manifolds for the frozen reac-
tants considered thus far (stoichiometric propane–
air, 50 per cent EGR) and the corresponding
equilibrium combustion products are shown in
Fig. 3. In both cases, the mixture’s internal energy
increases with increasing entropy and decreasing
volume, at slopes equalling the mixture temperature
T and pressure P, respectively. Isotherms are shown
on the figure as dashed lines. The reactant isotherms
coincide with the constant-U contours under the
assumption of ideal gas behaviour. The product
isotherms diverge at high internal energy and
volume owing to dissociation.
A common reference state and set of reference
species from the NASA thermochemical database are
used to account for the energy associated with
chemical bonds for both the reactant and product
species [19]. Graphically, this means that both
manifolds can be plotted on the same set of U, S,
and V axes, as shown in Fig. 4. Elements of the
volume-constrained fuel–air cycle are also shown in
this figure. They include:
(a) the constant-entropy curves on the manifolds,
for isentropic reactant compression and pro-
duct expansion;
Int. J. Engine Res. Vol. 9
458 K-Y Teh, S L Miller, and C F Edwards

Fig. 3 The fundamental relation manifolds U 5 U(S, V) for (a) the frozen mixture of fuel
(propane), air, and EGR; and (b) the equilibrium products of combustion

(b) the transition (or ‘jump’) across the manifolds
at the same volume and internal energy, for
constant-volume combustion;
(c) the constant-UV equilibrium trajectory on the
product manifold, to which the actual system
trajectory is attracted.
The projection of these lines onto the U, S bounding
plane closely approximates the trajectories shown in
Fig. 2.
The strategy for minimizing exergy destruction
associated with combustion is evident in Fig. 4,
which shows the reactant and product manifolds
approaching each other at high internal energy.
Therefore, the reacting mixture needs to be steered
towards a thermodynamic state with higher energy,
such that subsequent combustion (i.e. the jump to
the product manifold) incurs a smaller entropy
increase, or equivalently, destroys less exergy. The
magnitude of this destruction term is proportional to
the distance between the two manifolds along the S
axis. Its contour map on the U, V bounding plane is
shown in Fig. 5. The reactant isentrope (at entropy
S 5 Si) and isobar (at pressure P 5 Pi 5 1 atm) passing
through the initial mixture state are also included in
the figure for reference. For example, the figure
shows that complete combustion of the reactants
after a 20:1 isentropic compression destroys 15 per
cent of the fuel exergy supplied to the engine. This
amounts to a two-fifths reduction from the 26 per
cent exergy destruction incurred if the reacting
mixture is not compressed.

Fig. 5 The contour map for entropy generation due to

constant-UV combustion of a propane/
air mixture with EGR. The corresponding
Fig. 4 Optimal combustion cycle trajectory on the U, fractions of fuel exergy XC3 H8 destroyed are in
S, and V axes parentheses

Int. J. Engine Res. Vol. 9 JER01508 F IMechE 2008

 Thermodynamic requirements for maximum IC engine cycle efficiency. Part 1
It is important to recognize that the amount of
exergy destroyed is strongly dependent on the
internal energy of the fuel–air mixture just prior to
combustion. Of far less significance is the volume at
which combustion occurs, since the contours are
sloped only slightly along the V axis. This means that
the strategy for minimizing exergy destruction is less
a matter of reducing the reactant mixture volume,
and more a matter of raising its internal energy. For
the adiabatic engine model under discussion, this
strategy takes the form of reactant compression
simply because boundary work is the only permis-
sible mode of energy transfer into the closed system;
this need not be the case in general. For instance, if
heat transfer is permitted, Fig. 5 indicates that the
same two-fifths reduction in exergy destroyed (from
26 to 15 per cent of fuel exergy supplied) can also be
attained by preheating (isobarically) the reactant
mixture to 1450 K, rather than by compressing it
(isentropically) through a 20:1 volume ratio. The
excessive temperatures upon preheating or com-
pression are artifacts of the high initial reactant
temperature used in the illustrative examples [18],
retained here merely for consistency. The numbers,
while well past the autoignition point for most fuels,
do not obviate the more general conclusion that
exergy destruction can be reduced by internal energy
increase by either mode of transfer. This is not to
say that the two approaches are equivalent in the
thermodynamic sense; for example, entropy transfer
also takes place during reactant heating but is absent
during adiabatic compression. The attendant issues
are discussed further in the companion paper [17].
Fig. 6 The contour map for entropy generation due to
constant-UV combustion of stoichiometric hy-
drogen/air mixture. The corresponding frac-
tions of fuel exergy XH2 destroyed are in
parentheses
JER01508 F IMechE 2008
459
Returning to the subject of exergy destruction by
constant-volume combustion, its functional depen-
dence on the state variables U and V can be
established analytically based on the reactant and
product fundamental relations in differential form, i.e.
Gibb’s equation (10). Consider the adiabatic combus-
tion of some quantity of reactants at fixed volume. The
resulting exergy destruction term is given by
Xdest ~T0 |½SP ðU, V Þ{SR ðU, V Þ

where both entropy terms are evaluated at the same
volume V and internal energy U. Any change in exergy
destruction can therefore be related, via equation (10),
to changes in these two variables
dXdest
~dSP {dSR
T0



1 1 P P PR
~ { dUz { dV ð11Þ
TP TR TP TR
Equation (11) indicates that the conclusions drawn
based on the contour map in Fig. 5 can be general-
ized as follows.
1. Change in internal energy, dU. For exothermic
reactions (which is the case for combustion of
common fuel–air mixtures), the product gas tem-
perature TP is greater than that of the reactants TR,
so (TP21 2 TR21) is negative. Therefore, raising the
internal energy of the reactants (dU . 0) necessarily
reduces the exergy destroyed during the constant-
volume combustion process that ensues (dXdest , 0).
2. Change in volume, dV. Variation of the destruc-
tion term with volume is less clear-cut, and
depends on the chemical system under consid-
eration. Assuming that the reactant and product
gas mixtures are ideal, then


PP PR R 
{ ~ SNj,P {SNj,R ð12Þ
TP TR V
noting that VP 5 VR 5 V for constant-volume com-
bustion. If the combustion process leads to a net
increase in total mole number (i.e. mole-producing
SNj,P 2 SNj,R . 0), reducing the volume at which it
takes place (dV , 0) will reduce the exergy de-
stroyed (dXdest , 0). This is the case for most fuel–
air systems, as exemplified by the propane–air
system considered thus far (with positively sloped
exergy destruction contours in the V axis direction
in Fig. 5). The converse – exergy destruction
decreases when combustion occurs at a larger
volume – is true if mole number decreases during
Int. J. Engine Res. Vol. 9
460 K-Y Teh, S L Miller, and C F Edwards
the process (i.e. mole-destroying SNj,P 2 SNj,R , 0),
typified by hydrogen combustion. Figure 6 shows
the corresponding map of exergy destruction
contours (negatively sloped along the V axis).
While the slope of the contour lines may be fuel
dependent, the basic message is unaltered: the
reactants need to combust at a high internal energy
state in order to minimize the exergy destroyed.
Comparing the two contour maps in Figs 5 and 6, it
may be concluded that the internal energy invest-
ment is best made in the form of reactant compres-
sion if the combustion process is mole producing
(i.e. along the isentrope in Fig. 5), and via reactant
heating if the reaction is mole destroying (along the
isobar in Fig. 6). However, the two approaches to
raising reactant internal energy have very different
second-law implications on the work extraction
stage of the engine cycle, as alluded to above and
elaborated in the companion paper [17].
4 EFFECTS OF REACTANT MIXING AND
IGNITION PHASING
The optimal solution for minimum entropy generation
due to combustion (sections 3.1 and 3.2) is exact only
under the assumption that the gas mixture is homo-
geneous. The subsequent analysis based on reactant
and product manifolds (section 3.3) further presumes
that the mixture remains chemically frozen prior to
combustion. However, these assumptions are incom-
patible with practical implementation of the optimal
combustion strategy – as noted earlier, the internal
energy of a premixed system cannot be raised indefi-
nitely without combustion taking place. Autoignition
sets a bound on the minimum entropy generation that
such a system must incur, as illustrated in Fig. 1.
Further reduction in entropy generation beyond
this limit, while possible, would require delaying
ignition of the reacting mixture to enable even
higher compression of reactants. Ignition delay can
be accomplished by modifying the chemical kinetics
of the system, e.g. by using fuel blends with higher
octane ratings. Ignition timing can also be controlled
via fuel injection in non-premixed or stratified-
charge, compression-ignition engines. In this case,
air (the oxidizer) is compressed separately to a high
internal energy state. Combustion does not com-
mence until fuel is introduced into the system, after
which the reaction rate is primarily determined by
the mixing process between fuel and air.
It is asserted here that, for the most part, these
dynamic strategies for ignition phasing do not affect
Int. J. Engine Res. Vol. 9
the thermodynamic analysis presented thus far for
minimum exergy destruction. This is clearly the case
with the switch to fuels with improved antiknock
properties, since the results in section 3 are applic-
able to all fuel species.
The case for direct-injection strategies requires
further explication. Obviously, the assumption of
mixture homogeneity no longer holds; some exergy
is destroyed owing to fuel vaporization and mixing
with air. Nevertheless, the thermodynamic require-
ment for exergy destruction minimization in this
instance can be deduced using reasoning that
mirrors that presented earlier for premixed systems.
First, it is observed that prior to mixing, fuel and
air can be considered as separate components in a
non-premixed system of reactants. Hence, the
internal energies, entropies, and volumes – all are
extensive variables – of the two components are
simply additive to yield variables U, S, and V for the
aggregate system. This also applies to multi-zone
modelling of IC engines, by summing the variables
for all discrete zones of the model. In the absence of
the homogeneous mixture assumption, however, the
set of variables U, S, and V are no longer related by
the reduced form of Gibbs’ equation (10) during the
mixing process. In fact, the entropy S of the
aggregate system at any given internal energy U
and volume V is not unique. Rather, it depends on
parameters such as the fuel injection duration,
extent of fuel–air mixing, etc. However, the value of
S will coincide with the homogeneous frozen
reactant mixture entropy upon complete mixing.
Stated another way, the fundamental relation
manifold UR(S, V) for premixed reactants introduced
in section 3.3 (e.g. Fig. 3(a)) serves as the attractor
manifold for the state trajectory of the composite
system as mixing proceeds, in the same way that
the equilibrium product manifold UP(S, V) (e.g.
Fig. 3(b)) is the thermodynamic attractor for the
state trajectory as combustion proceeds. Both
manifolds are shown in Fig. 7, along with one
constructed for air and 50 per cent EGR plus a
stoichiometric amount of propane at 25 uC, 1 atm
prior to mixing. The two reactant manifolds are
almost indistinguishable from each other, whereas
the product manifold is displaced further away along
the S axis, indicating that entropy generated due to
reactant-to-product transformation is far larger than
that associated with fuel mixing. Figure 7 suggests
that the strategy to carry out chemical reactions at
high internal energy states, for the purpose of
minimizing the subsequent exergy destruction due
to combustion, is readily extensible to non-premixed
JER01508 F IMechE 2008
 Thermodynamic requirements for maximum IC engine cycle efficiency. Part 1
systems. Table 3 illustrates this quantitatively by
showing that mixing entropy Sgen,mix often accounts
for less than 2 per cent of the exergy content for most
fuels. The entropy change Sfg due to liquid fuel
vaporization also tends to be small, e.g. 2.4 and
0.7 kJ/(kg fuel)21 K21 (2.4 and 0.5 per cent fuel
exergy) for ethanol and isooctane at their respective
boiling points. By comparison, the exergy destroyed
due to constant-volume combustion (also listed in
Table 3) ranges from 10 to 25 per cent of fuel exergy.
There are two plausible objections to the explana-
tion thus far with regards to the thermodynamics of
delayed combustion phasing, via diesel-like opera-
tion with direct or indirect fuel injection and
compression-ignition, for minimum combustion-
generated entropy. First, the order of magnitude
argument becomes less tenable when higher levels
of EGR are involved. For instance, Fig. 7 does not
take into account entropy of mixing between a fresh
charge of air and 50 per cent EGR, which as Fig. 8
indicates can approach one-fifth of entropy genera-
tion due to combustion if the exhaust is hot.
The second objection pertains to the assumption
that the gases are completely mixed as part of the
reactant preparation process, separate from the sub-
sequent chemical reaction step. A reasonable argu-
ment may be made that conventional diesel combus-
tion is substantially different from this scheme. In
Fig. 7 Manifold for a composite system of air and 50
per cent EGR before mixing with stoichiometric
propane at 25 uC, 1 atm, shown relative to the
well-mixed frozen reactant and chemically
equilibrated product manifolds
JER01508 F IMechE 2008
461
diesel operation, autoignition occurs near the inter-
phase regions – at stoichiometric or richer equivalence
ratios – between the fuel jet and the surrounding air.
Jet momentum and turbulence induce further mixing
of the reactants and control the subsequent rate of
combustion. Therefore, the preparation and reaction
steps should not be separately analysed.
Despite these differences, the current authors
assert that the optimal combustion strategy need
not be altered. The reason traces back to equations
(6) and (7), restated below
dUeq ~dU~{P dV ~{P dVeq ð6Þ
 
Teq dSeq ~dUeq zPeq dVeq ~ {PzPeq dV ð7Þ
These equations remain applicable for an adiabatic,
non-premixed system at pressure P. The energy
balances for different components (fuel, air, reac-
tant, and product mixtures at any given ratio) add up
to yield the overall balance dU 5 2P dV in equation
(6) involving internal energy U and volume V of the
aggregate system. (Again, the exact same argument
extends to multi-zone engine modelling by summing
the energy balances for all the zones.) Gibbs’
equation (7) also remains valid since, regardless of
whether the system is homogeneous or not, it is
constrained at the end of combustion by a unique
equilibrium product manifold. Therefore, the opti-
mal strategy – whether to compress or expand –
continues to be determined by comparing the
pressures P and Peq, and still reduces to minimizing
the equilibrium attractor entropy Seq.
5 EFFECTS OF LOSSES DUE TO ENGINE HEAT
TRANSFER
Aside from the chemical kinetic (autoignition)
limitation considered previously, materials issues
impose another set of constraints on the actual
execution of the strategy for exergy destruction
minimization. In particular, the melting points of
advanced materials today (e.g. near 1500 K for
nickel-based superalloys, or 1800 K for coated car-
bon–carbon composites [20]) are still far below the
combustion temperature of most fuel–air systems,
especially if the reactions are to take place at high
internal energy states. This material constraint
necessitates active cooling of the IC engine and
removes a significant fraction of energy from
the working fluid. Consequently, as much as
one-quarter of the exergy supplied to the system is
lost to the engine coolant. In other words, the
Int. J. Engine Res. Vol. 9
462 K-Y Teh, S L Miller, and C F Edwards

Table 3 Entropy generated, Sgen, due to fuel–air mixing and to constant-UV combustion, as well as the associated
exergy destruction Xdest (entropy values are in the units of kJ/(kg fuel)21 K21)
Xdest Xdest Xdest Xdest Xdest
ð250 CÞ{ ð1000 KÞ ð1:1Þ { ð20:1Þ ð50:1Þ
Fuel species* Sgen,mix (% Xfuel) Sgen,mix (% Xfuel) Sgen (% Xfuel) Sgen (% Xfuel) Sgen (% Xfuel)
Hydrogen 8.5 (2.2) 14.7 (3.8) 66.9 (17.1) 38.6 (9.9) 31.7 (8.1)
Methane 1.7 (1.0) 3.0 (1.8) 41.0 (23.5) 27.6 (16.6) 24.1 (13.9)
Ethanol 0.7 (0.7) 1.6 (1.6) 25.2 (25.5) 17.8 (18.0) 15.8 (15.9)
Propane 0.8 (0.5) 1.9 (1.2) 40.4 (24.9) 28.1 (17.7) 25.9 (15.2)
Isooctane 0.4 (0.2) 1.5 (0.9) 40.6 (25.6) 28.8 (18.2) 25.6 (16.1)

*All species are taken as ideal gases. Reactions are with stoichiometric air.
{
Entropy generation due to mixing of fuel at 25 uC with stoichiometric air at the same temperature or at 1000 K (superscripted as such), and
the equivalent fraction of fuel exergy destroyed.
{
Entropy generation due to constant-UV combustion of reactants (initially at 25 uC, 1 atm) before, as well as after, compression
(superscripted 1:1, 20:1, and 50:1 respectively), and the equivalent fraction of fuel exergy destroyed.

Ðt
combustion process is far from adiabatic, which runs where tif dQ is the total heat loss from the engine PE
counter to the dynamical system model analysed over the time interval, while SR,i and SP,f denote,
above. respectively, the initial reactant and final product
If it is assumed that all the exergy transferred to the entropies within the engine. The requirement of
coolant is destroyed via coolant heat transfer to the complete combustion has thus been incorporated
surroundings, and not recovered via compounding, into the expression.
the overall exergy destruction for the piston engine Not surprisingly, equation (13) shows that the
Total
(denoted PE) and its cooling system (CS) is then exergy destruction Xdest consists of both a chemical
component and a heat loss component. Lowering
Total PE CS
dXdest ~T0 dSgen zT0 dSgen the overall destruction term therefore requires care-


 ful management of both combustion and heat
dQ 1 1
~T0 dSz zT0 { dQ transfer processes. For one thing, it is no longer a
T T0 T straightforward matter of decreasing the final pro-
duct entropy SP,f, since that may be accomplished at
or, when integrated over some time interval [ti, tf]
the expense of enhanced heat loss from the engine.
ð tf Total
In fact, to solve the problem of Xdest minimization
Total
 
Xdest ~T0 SP,f {SR,i z dQ ð13Þ would entail specifying the heat transfer process
ti
which is, in thermodynamic terms, a path-depen-
dent (i.e. non-unique) function. This is not unlike
the challenge, mentioned in the previous section, of
determining mixing entropy in a unique, path-
independent manner. As an alternative to solving
the problem analytically (possible under very re-
strictive conditions [21]), here a numerical approach
to solving the related problem of expansion work
maximization for a non-adiabatic piston engine was
examined in [22]. In this study, the engine compres-
sion ratio was fixed, which sets a hard bound on the
maximum internal energy level to which the in-
cylinder gas mixture can be raised via compression.
The optimized solution is characterized by a slight
reduction in heat loss during the compression
process, which leads to combustion at a marginally
higher internal energy state.
Fig. 8 Comparison between the entropy generated In other words, to the extent that heat loss can be
due to mixing of stoichiometric propane and Total
kept low, Xdest minimization reverts to the question
air (both at 25 uC, 1 atm) with varying amounts
of EGR (at 25 uC or 600 K, 1 atm), and the
of how to transform reactants to products in the
entropy generated during combustion of most efficient (i.e. with the least loss) manner, and
the resulting reactant mixture (after 20:1 the thermodynamic results of previous sections once
compression) again apply. Operating a high-efficiency combustion

Int. J. Engine Res. Vol. 9 JER01508 F IMechE 2008

 Thermodynamic requirements for maximum IC engine cycle efficiency. Part 1
engine necessarily entails carrying out the combus-
tion process at the highest possible energy state,
such that the constant-UV entropy change from
reactants to products is minimized. After all, relaxing
the requirement of adiabatic engine operation does
not invalidate the second-law principle that a closed
combustion system that is not in equilibrium always
seeks to maximize its constant-UV entropy.
There are many approaches to reducing engine
heat loss, such as wall insulation and other low-heat-
rejection concepts, lowering of the combustion
chamber surface-to-volume ratio (as in large diesel
engines), etc. A thorough review of these concepts is
beyond the scope of this paper, and the reader is
referred to other publications for detailed discus-
sions, for example references [8] to [10], and [23].
Peak combustion temperature may also be reduced
via dilution. A thermodynamic discussion of this
reactant preparation strategy is deferred to the
companion paper [17].
To summarize, while the system homogeneity and
adiabatic assumptions are essential for the dynami-
cal system control problem of minimum exergy
destruction to be solved exactly in reference [18],
the thermodynamic conclusions that can be drawn
from the optimal solution remain valid when the
assumptions are omitted. Equilibrium entropy Seq
minimization, through steering of the reactants to
the highest possible internal energy state before
reaction, is shown to be a general strategy for
minimizing the exergy destroyed during combus-
tion.
6 CONCLUSIONS
This is the first of a two-part paper in which the
strategies for maximizing expansion work output
from the IC engine are investigated. The discussion
focuses on the fundamental thermodynamic re-
quirements for the optimal engine operating cycle.
Some related implementation issues are also con-
sidered within this context, including reactant mix-
ing, ignition phasing, and engine heat loss.
Underpinning all analyses and conclusions pre-
sented in this article is the optimal control solution
for minimum exergy destruction due to combustion
in a homogeneous, adiabatic piston engine model
[18]. In thermodynamic terms, that solution reduces
to a strategy of minimizing the entropy of the
constant-UV equilibrium to which the chemical
system is attracted. For many systems, this strategy
is well approximated by the constant-volume com-
bustion cycle. However, the authors’ assertion is
JER01508 F IMechE 2008
463
much stronger than the well-known result – that the
constant-volume combustion cycle has higher effi-
ciency than the constant- or limited-pressure com-
bustion cycles – because the assertion is based upon
optimization and consideration of all possible
engine cycles.
Two important implications of the optimal solu-
tion are that:
(a) the reactant and product thermodynamic states
at the start and the end of combustion, as
opposed to chemical kinetics or other non-
linear dynamics during combustion, determine
the minimum exergy destruction due to com-
bustion;
(b) the optimal IC engine operating cycle (i.e. the
engine architecture) is composed of separable
elements of reactant preparation, combustion,
and work extraction from the products.
Based on the first finding, the thermodynamic
properties of the combustion system in its frozen
reactant and equilibrated product states are exam-
ined (by considering the respective fundamental
relation manifolds) to quantify the exergy destroyed
due to constant-UV combustion. Exergy destruction,
Xdest, is shown to be only mildly dependent on the
reactant mixture volume V, but a strong function of
its internal energy U at the point of combustion. In
particular, raising the internal energy necessarily
lowers exergy destruction because combustion is
exothermic. Therefore, the destruction term can only
be reduced by work and/or heat transfers into the
closed system, i.e. gas compression, heating, or some
combination of the two.
This result is readily extensible to non-premixed
and non-adiabatic systems. For non-premixed sys-
tems, exergy destruction from liquid fuel evapora-
tion and mixing are an order of magnitude below
that due to combustion. This is not the case with
respect to exergy destruction due to heat loss for
non-adiabatic systems. Nevertheless, provided that
heat loss can be kept low (or at least not exacer-
bated), then equilibrium (product) entropy Seq
minimization, through steering of the reactants to
the highest possible internal energy state before
reaction – following what may be called the ‘extreme
state’ principle – remains the general strategy
for minimizing the exergy destroyed during
combustion.
The second finding above implies that the remain-
ing elements of optimal IC engine architecture – i.e.
the reactant preparation and product expansion
(work extraction) processes – can be separately
Int. J. Engine Res. Vol. 9
464 K-Y Teh, S L Miller, and C F Edwards
analysed from the standpoint of managing the
associated exergy transfers so as to maximize the
overall engine cycle efficiency. The exergetic and
efficiency implications of these processes will be
discussed in the companion paper [17].
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APPENDIX 1
Notation
R̄ universal gas constant,
8.314 kJ/kmol21 K21
JER01508 F IMechE 2008
 Thermodynamic requirements for maximum IC engine cycle efficiency. Part 1
X exergy
Dr property change from reactants to
products
Subscripts
eq chemical equilibrium state (at con-
stant U, V)
f final (exhaust) state
i initial state
j property of species j
P product state
R reactant state
0 environmental (dead) state
APPENDIX 2
Notes on the illustrative examples
The thermodynamic analyses and discussions pre-
sented in this paper are fundamental in nature, and
are not dependent on specific engine parameters,
e.g. the choice of fuel, stoichiometry, or compression
ratio. For consistency, and without loss of generality,
most of the illustrative examples used are based on
the same chemical system first considered in
reference [18]. (Parameters used in that paper, in
turn, approximate the single-cylinder homogeneous-
charge, compression-ignition research engine para-
meters in reference [24].)
The system initially comprises a stoichiometric
propane–air mixture diluted with 50 per cent EGR
(complete-combustion products only)
C3 H8 z5ðO2 z3:76N2 Þzð3CO2 z4H2 Oz18:8N2 Þ
ð14Þ
at temperature Ti 5 562 K and pressure Pi 5 1 atm.
The initial temperature is chosen such that auto-
ignition occurs close to top centre upon adiabatic,
13:1 slider-crank compression at 1800 r/min. This
JER01508 F IMechE 2008
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465
system, its associated fundamental thermodynamic
relation manifolds, and its variants are used to
illustrate the thermodynamic implications of mini-
mum entropy generation due to combustion (Figs 1
to 5, and 7).
Figure 6 in section 3.3 shows how entropy genera-
tion varies with the volume at which adiabatic
combustion takes place for a hydrogen–air system
(with decreasing system mole number from reactants
to products, SNj,P 2 SNj,R , 0), to be contrasted with
Fig. 5 for the above-mentioned propane–air system
(with increasing mole number, SNj,P 2 SNj,R . 0). The
hydrogen–air system is stoichiometric
H2 z0:5ðO2 z3:76N2 Þ
and is initially at temperature Ti 5 298 K, pressure
Pi 5 1 atm.
Figure 7 in section 4 considers propane (denoted
here by subscript ‘1’) separately from the remaining
species listed in equation (14), i.e. stoichiometric
proportion of air with 50 per cent exhaust (subscript
‘2’). The unmixed reactant manifold is thus con-
structed by summing the internal energy, volume,
and entropy for propane (U1, V1, S1) at fixed T1 5
25 uC, P1 5 1 atm, with those for the air–exhaust
mixture (U2, V2, S2) at varying T2, P2.
The same approach applies when comparing
entropy generated due to mixing versus combustion
in Fig. 8. The mixing entropy arises when separate
components of propane and air (in stoichiometric
proportion, T 5 25 uC, P 5 1 atm) as well as combus-
tion products (varying residual fraction, T 5 25 uC or
600 K, P 5 1 atm) are combined.
The NASA thermochemical database [19] is used
in all the calculations, as is the GRI-Mech 3.0 natural
gas combustion mechanism [25] when reaction
kinetics are involved, e.g. Figs 1 and 2. The calcula-
tions are carried out using Cantera, an open source
program for chemical kinetics and thermodynamic
simulations [26], in conjunction with the computing
software MATLAB.
Int. J. Engine Res. Vol. 9