Energy 26 (2001) 705722 www.elsevier.

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Comparative second-law analysis of internal combustion engine operation for methane, methanol, and dodecane fuels
C.D. Rakopoulos, D.C. Kyritsis
*

Internal Combustion Engines Laboratory, Dept. of Mechanical Engineering, National Technical University of Athens, 9 Heroon Polytechniou Str., Zografou 15780, Athens, Greece

Abstract A method for both combustion irreversibility and working medium availability computations in a highspeed, naturally-aspirated, four-stroke, internal combustion engine cylinder is presented. The results of the second-law analysis of engine operation with n-dodecane (n-C12H26) fuel are compared with the results of a similar analysis for cases where a light, gaseous (CH4) and an oxygenated (CH3OH) fuel is used. The rate of entropy production during combustion is analytically calculated as a function of the fuel reaction rate with the combined use of rst- and second-law arguments and a chemical equilibrium hypothesis. It is shown theoretically that the decomposition of lighter molecules leads to less entropy generation compared to heavier fuels. This is veried computationally for the particular fuels and the corresponding decrease in combustion irreversibility is calculated. Special reference is made to the effect of the lower mixing entropy of the exhaust gas of an oxygenated fuel (CH3OH) as a contribution to the discussion of the advantages and disadvantages of the use of such fuels. 2001 Elsevier Science Ltd. All rights reserved.

1. Introduction The limitations imposed by the second law of thermodynamics on the operation of thermal engines are among the most fundamental conclusions of classical thermodynamics. However, quantitative second-law analysis is much less frequently used to study these devices than its rstlaw counterpart. Recent studies [1,2] show that almost 1/3 of the energy of a fossil fuel is destroyed during the combustion process in power generation. This has caused a renewed interest in exergy analyses, since effective management and optimization of thermal systems is emerging as a major modern technical problem [3]. The equations for the second law analysis of thermodyn* Corresponding author. Present address: Yale University, Dept. of Mechanical Engineering, 9 Hillhouse Ave, Room 117, New Haven, CT 06520, USA. Fax: +1-203-432-7654. E-mail address: dimitrios.kyritsis@yale.edu (D.C. Kyritsis).

0360-5442/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved. PII: S 0 3 6 0 - 5 4 4 2 ( 0 1 ) 0 0 0 2 7 - 5

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Nomenclature afv cv, cp G g H h I N0 NO2 P Q R S s T U u V Injected fuel molar availability (J/kmol) Molar heat capacity (J/kmol K) under constant volume (or pressure) Gibbs free energy (J) Molar Gibbs free energy (J/kmol K) Enthalpy (J) Molar enthalpy (J/kmol) Irreversibility (J) Molar quantity (kmoles) in the dead state Molar quantity (kmoles) of oxygen Pressure (Pa) Heat (J) Universal gas constant (8314 J/kmol K) Entropy (J/K) Molar entropy (J/kmol K) Temperature (K) Internal energy (J) Molar internal energy (J/kmol) Volume (m3)

Greek Symbols a b g Number Number Number working of atoms of carbon in the fuel molecule of atoms of hydrogen in the fuel molecule of atoms of oxygen in the fuel molecule medium availability (J)

Subscripts 0 fv i pr re Dead state Fuel liquid Fuel vapor Species in the working medium Prepared fuel Reacted fuel

Superscript 0 Dead state

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Abbreviations ATDC After top dead center BTDC Before top dead center CA Crank angle (degrees)

amic systems are presented and discussed thoroughly in Ref. [2] and are used to analyze the operation of power plants in Refs. [4] and [5]. For internal combustion engines, early work [6,7] on the evaluation of the global engine operation using of second-law techniques was followed by detailed availability and irreversibility calculations during the engine cycle [810]. Second-law arguments have been used to evaluate novel engine concepts [6], to investigate the effect of operating parameters on efciency [9], and more recently, to reveal interesting aspects of the transient engine operation [11]. The overall energy and availability balance during an engine cycle are studied analytically in Refs. [12] and [13]. In this article, we present a generalization of the method developed in Ref. [9] for the secondlaw analysis of the operation with dodecane fuel and use it to analyze the operation with alternative fuels. Specically, the cases of a light gaseous fuel (CH4) and an oxygenated (CH3OH) fuel were studied. Using the extensive experimental data available for the case of n-dodecane (n-C12H26) injection, which typically represents the diesel fuel in the study of automotive or smaller size diesel engines [14,15], the fuel reaction (combustion) rate is determined [16]. Combustion irreversibility is analytically calculated as a function of the fuel reaction rate with the use of second-law analysis and a chemical equilibrium hypothesis. The differential variation of working medium availability is computed throughout the engine cycle. Both quantities can be integrated during the cycle to yield a total combustion loss and the exhaust gas availability. The combustion loss is a measure of the entropy created during combustion, which can not be revealed by rst-law analysis. The exhaust gas availability contains more information than its enthalpy counterpart as far as the possible operation of exhaust gas heat recovery devices is concerned. Such devices include exhaust gas turbines and Rankine bottoming cycles, and are restricted in their operation by second-law arguments, in a manner that can not be evaluated by rst-law analysis. 2. Experimental facility modeling approach The engine used to study the operation with dodecane fuel was a Lister LV1, direct-injection diesel engine. This was a four-stroke, naturally-aspirated, air-cooled engine with a bowl-inpiston combustion chamber having a bore of 85.73 mm, a stroke of 82.55 mm and a rod length to crank radius ratio of 3.6. The compression ratio was 18 and the nominal speed range was between 1000 and 3000 rpm. A three-hole injector nozzle (hole diameter of 250 m) was used for dodecane injection. It was located near the combustion chamber center with an opening pressure of 190 bar. The full load conditions correspond to equivalence ratio of j=0.625, injec-

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tion timing of 22CA BTDC and injection duration of 24CA. Measurements were taken for equivalence ratios 0.600 and 0.470 and injection timings of 19, 22 and 25CA BTDC. A detailed description of the experimental setup and the data acquisition interface has been presented in Refs. [8,9,14,16]. A single-zone model was used to simulate the engine operation. The most important assumptions were the following: 1) The working medium was considered, in general, to be a mixture of 10 species (O2, N2, CO2, H2O, H2, OH, NO, CO, O, H) and fuel vapor; 2) All 10 species were considered as ideal gases; 3) Blowby was ignored; 4) The residual gas fraction was taken equal to 10% independent of conditions of operation, which was a reasonable assumption for the operating parameters described above [9,16]. Experimental data were available only for dodecane injection. Computationally, the cases of methane (CH4) and methanol (CH3OH) injection were also investigated. Proper processing of the experimentally acquired indicator diagrams can yield the preparation and reaction rates of the fuel, as described in detail in Refs. [16] and [18]. The preparation stage involved vaporization of the fuel, its superheating to the temperature of cylinder gases and mixing with the oxidizer so that a ammable mixture forms in certain regions of the combustion chamber. The intuitive assumption that preparation times for gaseous (CH4) injection must be much shorter than the ones for liquid injection is not correct [19]. Summarizing the data processing algorithm here for the purpose of completeness, we can state that it correlates the differential change in mixture composition to the differential of the natural logarithm of pressure in the combustion chamber. Similar but signicantly simpler approaches to the calculation of an effective burning law from pressure data are presented in Refs. [14] and [20]. The reacted and prepared fuel quantities computed are used as input to the equilibrium code described below. The tting of a Wibbe function [20] to the reacted fuel distribution makes this analysis much simpler. As Fig. 1 shows, the Wibbe function offers a exible and accurate approximation to the reacted fuel quantity. The four coefcients of the function are calculated using a least squares t. It should be mentioned that the crank angle at the start of combustion must be located for such a formulation to work. This poses a difculty in modeling diesel combustion since ignition is not forced (e.g. by a spark plug). The onset of combustion could, in principle, be calculated. However, this complicates the model signicantly without adding any value to the present study. The angle of onset of combustion is treated as a parameter of the Wibbe function determined by the least square algorithm. Once the molar quantities Npr and Nre of prepared and reacted fuel, respectively, are known, determination of the thermodynamic condition of the working medium requires calculation of pressure P, temperature T and the molar quantities Ni of the aforementioned ten species. This calculation was achieved through the solution of 12 equations consisting of: The ideal gas equation of state for the mixture:
11

PV RT
i 1

Ni

(1)

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Fig. 1. Approximation of the reacted fuel quantity by a Wibbe function.

The energy balance for a closed system of variable volume:

11 11

dQ dNpr(hfl hfv) pdV

i 1

uidNi dT
i 1

Nicvi dNprhfv

(2)

The rst two terms on the left-hand side are the heat inux. The third term is the work output of the system. The rst two terms on the right hand side are the change in internal energy of the working medium due to the change of its composition and temperature respectively. The third term is the enthalpy inux to the working medium due to fuel vaporization. The volume is calculated analytically as a function of the crank angle. The thermodynamic properties are computed as a function of T by polynomial ttings to the data of JANAF Thermochemical Tables [21]. Heat transfer through the system boundary is calculated as a function of T, the thermodynamic properties of the working medium and the wall temperature using Annands formula, as described in Ref. [9]. The molar quantities Ni are calculated using a chemical equilibrium assumption. Specically, we assume that the following six reactions among the above 10 species were in equilibrium: H22H

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O22O

H2 O22OH

N2 O22NO

2H2 O22H2O

2CO O22CO2 At each crank angle, equilibrium equations for these six reactions as well as atom number conservation equations for the atoms of C, H, O and N, constitute a 1010 system of equations which can be solved for Ni. This is a generalization of the procedure described in Refs. [9] and [15] for dodecane, where the validity of the chemical equilibrium assumption is discussed. In general, the chemical equilibrium assumption is not valid for the formation of pollutants, especially NO at the late stage of the expansion stroke when the chemical kinetics freezes yielding quantities of NO at the exhaust much higher than the equilibrium values [17,20]. Given the fact that the quantities of pollutants are in any case small, the main conclusions of this work are not affected.

3. Second-law analysis 3.1. Concepts and denitions Availability of a system is dened as the maximum work that can be produced from the system through interaction with its surroundings during a reversible transition to a state of thermal, mechanical, and chemical equilibrium with its environment, and while heat is exchanged during the transition only with this environment. This state of equilibrium is dened as the dead state of the system and it depends on the pressure P0, the temperature T0 and the composition of the environment. In the present study, the environment is dry atmospheric air with P0=1 bar and T0=298 K. Thermal equilibrium is achieved when there is no heat exchange between the system and the environment, i.e. when the system is at temperature T0. Similarly, mechanical equilibrium is achieved when there is no work exchange between the system and its environment. Chemical equilib-

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Fig. 2. The closed system under consideration and the related availability streams.

rium is achieved when no system component can react with the environment. For the present case, this means that in the dead state all the 11 species of the working medium have been either oxidized or reduced to N2, O2, CO2, and H2O. It is shown in Refs. [2224] that the availability of a closed system is equal to U P0V T0S G0 (3)

A direct consequence of the above denition is that when a differential amount of reversible work dW=(P P0)dV is extracted from a system, its availability is reduced by exactly that amount. Similarly, when a differential amount of heat dQ is supplied to the system at temperature T, the system availability is increased by an amount dQ(1 T0/T). The system under consideration is shown in Fig. 2. It is a closed system, since only the part of the cycle from inlet valve closing to exhaust valve opening is considered. The only mass inux to the system is the prepared fuel, which takes place after injection. The differential availability uxes can also be seen in Fig. 2. On the basis of the availability balance, the differential variation of the working medium availability is given by d (P P0)dV [dQ dNpr(hfl hfv)](1 T0/T) dNprafv dI (4)

On the right hand side, the rst term is availability outux from the system in the form of work. The second term is availability input through heat ux and the third term is availability added to the system by the fuel vapor. The term dI makes Eq. (4) different from a conservation equation. During combustion working medium availability is destroyed and a differential amount dI of

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combustion irreversibility is produced. Similarly, during fuel preparation, there is availability destruction due to mixing, which is included in the calculation of afv, as shown later. From Eqs. (3) and (4), it can be seen that in order to calculate the combustion irreversibility, one has to determine the dead state and calculate afv. 3.2. Determination of the dead state For the system to reach the dead state at P0=1 bar and T0=298 K, all of the working medium constituents have to be either oxidized or reduced to N2, O2, CO2 and H2O. Knowledge of the precise mechanism with which this happens is not necessary for determination of the molar quantity of each of the four species in the dead state. Instead, one can write atom conservation relations of the type: NO1/2 N2 1/2 O2 This schematic representation has no meaning as a chemical reaction; it simply shows the relation of molar quantities between the working medium species and the molar quantities of N2 and O2 in the dead state. A similar relation for the complete oxidation of an oxygenated fuel vapor gives: CaHbOg (a b/4 g/2)O2aCO2 b/2H2O Finally, similar considerations for all species, yield the following relations for the composition of the dead state: N0 2=NN2+NNO/2 N N0 2=NCO2+aNfv+NCO CO N0 2=NO2(a+b/4g/2)Nfv+(NO+NNONH2NCO)/2+(NOHNH)/4 O N0 2O=NH2O+(b/2)Nfv+NH2+(NH+NOH)/2 H The differential variation of the G0 term is then given by:
4

(5)

dG0
i 1

dN0 gi(T0,P0) RT0ln i

N0 i N0 i

(6)

The second term of this sum corresponds to the entropy of mixing in the dead state. 3.3. Availability introduced to the system with the fuel vapor The fuel vapor availability consists of two parts. The rst part, usually termed thermal or thermo-mechanical part, is equal to:

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afv, thermomechanical hfv T0sfv g0 fv

(7)

This is the amount of availability introduced by the injected gas. A second part, usually termed thermo-chemical availability, is due to the ability of fuel to react and produce reactants of lower availability. For the calculation of the thermochemical availability, we consider the reaction of complete oxidation of the fuel in atmospheric air: CaHbOg ((a b/4 g/2)/0.21)(0.21O2 0.79N2)aCO2 b/2H2O [0.79(a b/4 g/2)/0.21]N2 It is shown [23], that the thermochemical availability is equal to the difference in Gibbs free energy between reactants and products at temperature T0 and pressure P0. It follows that: afv, thermochemical g0 ag0 2 (b/2)g0 2O (a b/4 g/2)g0 2 fv CO H O RT0ln aa(b/2)b/2ee a+b/4g/2)a+b/4g/2zz (8)

where the last term of the sum accounts for the difference in entropy of mixing between products and reactants, and e and z are dened as follows: e (a b/4 g/2)/0.21

z 0.79e a b/2 Adding Eqs. (7) and (8) we get for the total fuel availability: afv hfv T0sfv ag0 2 (b/2)g0 2O (a b/4 g/2)g0 2 RT0ln CO H O aa(b/2)b/2ee a+b/4g/2)a+b/4g/2zz

3.4. Calculation of combustion irreversibility If we substitute Eqs. (3) and (6) in Eq. (4) and subtract Eq. (2) multiplied by T0/T, we get: dI dNprafv [dQ dNpr(hfl T0 N c dT T i 1 i pi
11 4

T0 Ni T0 t dN (s Rln VdP hfv)] ) dNprhfv T 0i 1 i i T Ni

11

(9)

dN0g0i i
i 1

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The energy balance for the system can be reformulated in enthalpy terms as:
10 10

dQ dNpr(hfl hfv) VdP

i 1

hidNi hfv (
i 1

Nicpi Nfvcpfv)dT dNprhfv

(10)

Eq. (10) is the expression of the same energy balance as Eq. (2) reformulated in terms of enthalpy. If Eq. (10) is multiplied by T0/T and subtracted from Eq. (9), keeping in mind that the expression for gI is gi hi Tsi RTln(Ni/ it is shown that: dI T0 dN g Ti 1 i i
11 4

Ni)

dN0g0i dNpr[afv hfv(1 i

i 1

T0 )] T

(11)

This proves that the differential availability destruction is only a function of the differential change in mixture composition. It is interesting to note that one of the main mechanisms of irreversibility production, namely heat transfer, affects the nal result only indirectly since dI is not an explicit function of dQ. Irreversibility production due to uid viscosity, as discussed in Ref. [1], can not be calculated within the framework of the current single-zone analysis.

4. Results and discussion The availability balance during the engine cycle is presented for the dodecane injection case in Fig. 3. Only the closed part of the engine cycle is presented, i.e. the part from the closing of the intake valve to the opening of the exhaust valve. This is a balance between ve terms: working medium availability, availability transfer through work, availability transfer through heat, input of availability with the injected fuel, and destruction of availability (production of irreversibility). All ve terms are calculated independently as described earlier. The decit in the balance caused by the employed numerical scheme is of the order of 1% of the availability of the injected fuel. Since the availability input with the injected fuel starts and ends abruptly with the start and end of injection, respectively, it is expected that discontinuities in the derivative of the corresponding curve should appear. During fuel injection and preparation, there is a gradual fuel availability inux. It can be noted that there is a signicant loss of working medium availability during the fuel preparation. This is due to working medium cooling because of fuel vaporization. The production of irreversibility due to irreversible heat transfer during compression is negligible compared to the combustion irreversibility. In fact, signicant production of irreversibility takes place only after ignition. This may be due to insufcient modeling of heat transfer within the framework of a single-zone model and should be investigated further with the use of multi-zone models like the ones presented in Refs. [16,17]. It is reminded, however, that Eq. (11) shows that heat transfer affects combustion irreversibility only indirectly.

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Fig. 3.

Availability balance for operation with dodecane fuel.

No experiments were conducted with either methanol (CH3OH) or methane (CH4) injection, since this would involve re-design of the employed hardware well beyond the scope of this work. However, some characteristics of the availability balance can be used to extract useful information by substituting dodecane with alternative fuels in the employed code. Fig. 4 shows the effect of fuel reaction rate on combustion irreversibility. The fuel is dodecane, the equivalence ratio is kept constant and equal to 0.600, and the reaction rate is computationally modied in the code (increased and decreased by a factor of 3). As a result of this modication, only the detailed time evolution of the combustion irreversibility is drastically affected, whereas the total irreversibility production only varies by approximately 2%. Similar results hold for numerical modications of the preparation rate, and for the other terms of the availability balance described above. In the case of the alternative fuels examined here no experimental data are available for the calculation of the precise time history of the availability balance. The above analysis, though, shows that the total value of each of the terms of this balance at the end of the closed cycle is mainly a function of the total quantity of the injected fuel and not of the detailed preparation and reaction rates. The comparison of these total values for the three fuels is meaningful if it reveals differences much higher than 25% of the total combustion irreversibility. If we substitute CH3OH and CH4 in the employed code as injected fuels and keep the equivalence ratio equal to 0.600 as in the dodecane case, we can compute availability balances like the ones shown in Figs. 5 and 6. The mass ow rate of air is also kept the same for all three fuels. This is one simple baseline that can be used for the comparison. However the methodology to be presented here can be used for more complicated reference criteria, e.g. same load (i.e. indicated mean effective pressure), equivalent pollutant emissions etc. Same equivalence ratio and air quantity means approximately same load since the stoichiometric air/fuel ratios and the lower

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Fig. 4. Effect of numerical increase and numerical decrease of the reaction rate by a factor of 3 on combustion irreversibility.

Fig. 5. Availability balance for operation with methane fuel.

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Fig. 6. Availability balance for operation with methanol fuel.

heating values of the examined fuels do not differ signicantly. In Ref. [9] the effect of load on the availability balance during operation with dodecane is studied. In order to be conclusive about the potential advantages of alternative fuels from the second-law-analysis point of view, these fuels will have to be implemented experimentally so that the conditions of optimal operation are determined. Then the operating cycles at the optimal conditions for each particular fuel will have to be compared with each other according to the procedure described here. The detailed time evolution of each of the terms of the presented balances of Figs. 5 and 6 is a function of the precise preparation and reaction rates of CH3OH and CH4, which can only be determined from experimental data. However, the exhaust gas availability (available for heat recovery devices) and the total combustion irreversibility can be approximated without the knowledge of this data, provided that reaction has been completed reasonably early relative to the exhaust valve opening timing. Figs. 79 show the comparison between injected fuel availability, exhaust gas availability and combustion irreversibility for the three fuels, for injection with the same equivalence ratio. It can be seen that the injected fuel availability is signicantly higher for the methanol case. Because of the oxygen content of the fuel, higher molar quantity of fuel is necessary for combustion with the same equivalence ratio. Comparing the results for methane and n-dodecane, we observe a signicant decrease of combustion irreversibility for methane combustion. This is in agreement with the theoretical expectation that the decomposition of the larger n-dodecane molecule during chemical reaction should create higher entropy increase than the decomposition of a lighter methane molecule. To illustrate this point, we consider the combustion of parafns in oxygen, although similar arguments hold for any fuel and oxidizer. In general, a parafn would burn according to the scheme: CnH2n+2 (1.5n 0.5)O2nCO2 (n 1)H2O

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Fig. 7. Injected fuel availability for three alternative fuels.

Fig. 8.

Exhaust gas availability for three alternative fuels.

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Fig. 9. Combustion irreversibility for three alternative fuels.

The entropy of mixing of reactants and products respectively are: Sreactants=R(1ln( 1 1.5n+0.5 )+1.5n+0.5)ln( )) 1.5n+1.5 1.5n+1.5

n n+1 +(n+1)ln( )) Sproducts=R(nln( 2n+1 2n+1

(12)

If, again without loss of generality, we assume that n is sufciently large so that n+1 n, 1.5n+1.5 1.5n+0.5 1.5n and 2n+1 2n we can derive: Sproducts Sreactants R(2nln2 ln(1.5n)) (13) which is obviously an ascending function of n. The decrease of combustion irreversibility is even higher for the case of oxygenated fuel. This can be explained as follows: The entropy of mixing is calculated as Smixing=R Niln(Ni/ Ni) and is maximum when the mixture fractions of all the components of a mixture are equal. Small entropy of mixing means high availability of reactants and signicant availability loss during the transition to products. In the case of hydrocarbons, the mixture of reactants consists almost totally of air and has a small entropy of mixing. In the methanol case, the fuelair molar ratio in the reactants is higher because of the oxygen content of methanol. This means higher entropy of

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mixing of the reactants and less entropy production during the transition to products. It can be also observed that, in the methanol case, the availability of exhaust gas is increased in absolute terms. This is due on one hand to the smaller production of entropy during combustion and on the other to the fact that, for the same equivalence ratio, the injected fuel availability is higher for methanol injection. As a fraction of the injected fuel availability, the exhaust gas availability is also increased in the methanol case as it can be seen from Figs. 7 and 8. A second-law efciency can be dened as the ratio of extracted work over injected fuel availability. It should be stressed that this ratio is only calculated here for the closed part of the cycle and is not the second-law efciency of the full cycle. Comparison of the efciency for the three cases is presented in Fig. 10. It seems that the use of alternative fuels leads to better secondlaw efciency. However, especially as far as the comparison between methane and methanol is concerned, the difference is small so that conclusions should be drawn with caution given the assumptions of the current analysis. Methanol vapor, for instance, was assumed to be an ideal gas but this is only a coarse approximation, given the fact that the critical point of methanol is 513 K and 8.1 bar. More accurate modeling of the thermodynamic properties of methanol may alter the injected fuel availability. Moreover, for the accurate calculation of the irreversibility created during combustion, an accurate computation of methanol combustion kinetics is necessary. It would also be interesting to investigate the effect of the fact that this is a single-zone analysis by incorporating the current arguments in multi-zone codes, following e.g. Ref. [11]. Revisiting the above assumptions may yield more accurate information about the advantages Figs. 69 imply for oxygenated fuels. However, the

Fig. 10. Second-law efciency for three alternative fuels.

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main point remains that entropy increase during combustion is smaller for such fuels because of the lower mixing entropy of the mixture of reactants. 5. Conclusions A method for the analytic calculation of irreversibility and exhaust gas availability is generalized and used to evaluate alternative fuels in a high-speed, direct-injection, naturally-aspirated, four-stroke diesel engine. Combustion irreversibility is shown to be the main source of irreversibility during the engine operation and its differential variation is calculated as an analytic function of the differentials of the molar quantities of the constituents of the working medium. Decrease in combustion irreversibility is achieved with the use of a lighter (methane) and, even more, of an oxygenated (methanol) fuel for the same equivalence ratio of operation. This is due to the combustion characteristics of these fuels which involve lower entropy of mixing in the combustion products. So far, the driving force for the study of alternative fuels has been to decrease pollutant emissions. Given the increasing interest in conservation, the use of such fuels may be seen in a different perspective since there are indications that it involves a more effective use of the chemical energy of the fuel. References
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