Fuel 83 (2004) 23132321 www.fuelrst.

com

Inuence of fuel and air/fuel equivalence ratio on the emission of hydrocarbons from a SI engine. 2. Formation pathways and modelling of combustion processes
E. Zervasa,*, X. Montagnea, J. Lahayeb
a b

trole, 1 et 4 avenue du Bois Pre au, Rueil-Malmaison cedex F-92500, France Institut Franc ais du Pe Institut de Chimie des Surfaces et Interfaces, 15 rue Jean Starcky, Mulhouse cedex F-68057, France Received 19 January 2004; revised 22 June 2004; accepted 24 June 2004 Available online 7 August 2004

Abstract A spark ignition engine was used to study the impact of fuel composition and of the air/fuel equivalence ratio on exhaust emissions of specic hydrocarbons. The fuel blends used contained eight main hydrocarbons and four oxygenated compounds. The identication of each exhaust pollutant fuel precursor is already done. After this identication, several models correlating the exhaust concentration of these pollutants with the fuel composition are presented on each air/fuel equivalence ratio. Based on the above ndings, the main formation paths for the formation of each exhaust pollutant are proposed. q 2004 Elsevier Ltd. All rights reserved.
Keywords: Exhaust Emissions; Modelling; Specic Hydrocarbons

1. Introduction Correlations between fuel composition and exhaust emissions from spark ignition (SI) engines have been extensively researched for regulated pollutants ([14] and many others). However, exhaust hydrocarbons are a sum of several species, and the emissions of individual hydrocarbons have not been thoroughly investigated yet. In three previous works, we presented the inuence of fuel and of l on the emission of organic acids [5], alcohols and carbonyl compounds [6], and regulated pollutants (CO, total HC and NOx [7]) of a SI engine. Continuing this work, the inuence of the above parameters on the emission of specic hydrocarbons is now presented in two papers. The rst one [8] presents the experimental ndings of this study: the main precursors of each pollutant, the inuence of air/fuel equivalence ratio, the percentage of each pollutant

over total emitted HC, the relations with the fuel physical properties, the correlations of the emitted HC with other exhaust components, etc. Based on the results presented on the rst article, the second one is rstly focusing on the modelling between the emitted pollutants and fuel composition and secondly on the formation pathways of these pollutants. 2. Experimental section The experimental procedure is presented in the rst article of this study [8] and elsewhere [9]. 3. Results and discussion 3.1. Models A quantitative model relating the exhaust concentration (in ppmv) with the contents of the fuel components (in % of volume) is searched for each pollutant: Exhaust pollutantZ a!fuel component1Cb!fuel component2C/ (Table 1). All models presented here take also into account

e Cor* Corresponding author. Address: Renault-CTLL26060, 1, Alle nuel, F-91510 Lardy, France. Tel.: C331-6927-8477; fax: C331-69278292. E-mail address: efthimios.zervas@renault.com (E. Zervas). 0016-2361/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2004.06.028

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E. Zervas et al. / Fuel 83 (2004) 23132321

the composition of alkylate. Using all experimental points, the lines Predicted valuesZa1!experimental valuesCb1 are estimated. The r2 of the presented models are always higher than 0.91, with a1 very close to 1.0 and b1 very close to 0.0, indicating a very good accordance between predicted and experimental values. As methane and ethane are the nal products of a series of reactions, their exhaust concentration is not directly linked with the fuel composition and no such model is found. According to the ethylene model at stoichiometry, the majority of this pollutant comes from fuel octane (25.3%), hexane (19.6%), 1-hexene (18.2%) and cyclohexane (15.3%), followed by isooctane, ETB, 2-propanol and o-xylene. In accordance with the rst article [8], the main sources of ethylene are the straight chain hydrocarbons. The percentage of hexane and octane decreases with l, this of isooctane, o-xylene and ETB increases, while this of 1-hexene, cyclohexane and 2-propanol presents a maximum at lZ1.0. The increasing percentage at rich conditions indicates that the corresponding fuel components are cracking easier to give ethylene than the others under these conditions. At stoichiometry, the majority (80%) of acetylene comes from fuel benzene. As benzene is found in almost equal content in all fuels, exhaust concentration of acetylene is almost equal in all fuels [8]. All other sources are less important, their participation is 0.83.4% each. The percentage of benzene decreases with lambda (from 88.5% at lean conditions to 62.6% at rich ones), while this of all other compounds increases. The most important source of propylene at stoichiometry is fuel isooctane (24.1%), followed by 2-propanol (23.3%), 1-hexene (20.0%), octane (15.6%), hexane (13.3%) and cyclohexane (3.7%). The percentage of 2-propanol and isooctane presents a maximum at stoichiometry, this of hexane, cyclohexane and octane a minimum at the same point, while this of 1-hexene increases. A model linking the exhaust concentration of isobutane with fuel isooctane is constructed, but it is not very good, the r2 of the line Predicted valuesZa1!experimental valuesCb1, is only 0.743 (a1Z0.78 and b1Z0.44). The addition of MTBE or of a constant, or even of other fuel components, does not improve it, indicating that this pollutant must also have other sources not directly linked with the initial fuel composition. At stoichiometry, exhaust 1-butene is formed from fuel octane (36.3%), hexane (32.8%), hexene (21.2%) and isooctane (9.6%). The percentage of hexane decreases at rich conditions, this of isooctane and hexene presents a maximum at stoichiometry, while this of octane presents a minimum at the same point. Most of the half (55.6%) of exhaust isobutene comes from fuel MTBE and the rest from isooctane at lZ1.0, while the addition of other fuel components does not improve this model. The percentage of isooctane increases

at rich conditions, while this of MTBE decreases. Contrary to isobutane, MTBE clearly participates to the formation of isobutene. As the exhaust concentrations of cis and trans-2-butene are very low, no model linking them with fuel components is found. At stoichiometry, the quasi totality of exhaust isopentane comes from fuel isopentane, but isooctane also contributes by 1.01.7%. Lambda does not seem to inuence these contributions. The addition of other fuel components does not improve this model, indicating that fuels isopentane and isooctane are the only sources of this pollutant. At stoichiometry, the majority (82%) of exhaust benzene comes from fuel benzene; the other sources are ETB, toluene, o-xylene and cyclohexane. These percentages change with l: the specic weight of benzene decreases at rich conditions, this of the other three aromatics increases because of the dealkylation increase, while this of cyclohexane decreases. This model shows that the specic weight of fuel benzene is the most important, but the quantity of exhaust benzene of a commercial fuel comes principally from the other aromatics due to their high content in the fuel. Kameoka [10] presents the model BZ0.56BC0.05TC0.04XC0.08ETB (in C basis). In the case of exhaust toluene, the two-thirds of its concentration at stoichiometry come from fuel toluene; fuel o-xylene contributes with 26% and the rest comes from fuel ETB. Benzene is not statistically signicant for this model. These percentages change with l; the specic weight of toluene decreases at rich conditions, this of ETB globally increases, while this of o-xylene presents a maximum at stoichiometry. Kameoka [10] presents that exhaust toluene is linear with fuel xylenes and ETB. At lZ1.0, the 85% of exhaust ETB comes from fuel ETB; the rest comes from toluene and o-xylene. These percentages change with l; the specic weight of toluene and o-xylene presents a maximum at stoichiometry, while this of ETB presents a minimum value at the same point. The benzene is not statistically signicant to this model. Kameoka [10] presents that exhaust ETB is linear with fuel ETB. In a previous article [9], we proposed four models linking the exhaust concentration of 1,3-butadiene with fuel 1-hexene and cyclohexane, the concentration of exhaust 1-hexene with fuel 1-hexene and cyclohexane, the concentration of exhaust cyclohexane with fuel cyclohexane and the concentration of isopropylbenzene with fuel ETB. A closer analysis shows that four improved models are valid. At stoichiometry, more than the half of exhaust 1,3-butadiene comes from fuel cyclohexane (50.5%); the other sources are 1-hexene (19.7%), o-xylene (11.3%), octane (10.7%), isooctane (4.0%) and hexane (3.8%). The percentage of cyclohexane increases at rich conditions (from 31 to 61%), this of 1-hexene and octane decreases, while this of o-xylene, hexane and isooctane presents a maximum at stoichiometry. In the second case, at

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Table 1 Model coefcients for the ve air/fuel equivalence ratios used. Percentages of participation of each fuel component and r2, a1 and b1 of the lines Predicted valuesZa1!experimental valuesCb1 Pollutant, l Ethylene 1.25 1.11 1 0.91 0.83 Acetylene 1.25 1.11 1 0.91 0.83 Propylene 1.25 1.11 1 0.91 0.83 1-Butene 1.25 1.11 1 0.91 0.83 Isobutene 1.25 1.11 1 0.91 0.83 1,3-Butadiene 1.25 1.11 1 0.91 0.83 1-Hexene 1.25 1.11 1 0.91 0.83 Cyclohexane 1.25 1.11 1 0.91 0.83 Benzene 1.25 1.11 1 0.91 0.83 Toluene 1.25 1.11 1 Fuel component r2 0.917 a1 0.979 B1 4.338 23.3 21.1 19.6 17.3 16.5 0.967 0.967 1.576 0.9 1.3 2.0 2.5 3.9 0.940 0.950 0.948 22.7 19.4 13.3 13.9 16.4 0.943 0.970 0.021 51.9 46.1 32.8 31.8 31.9 0.953 1.04 1.07 42.2 42.8 44.4 47.2 48.6 0.940 0.958 0.110 0.0 0.9 3.8 3.3 1.9 0.953 0.909 0.273 64.83 68.01 71.07 71.8 71.56 0.965 0.982 0.259 27.14 24.00 27.20 27.81 28.44 75.7 78.4 80.4 85.6 88.6 4.7 4.8 2.2 1.4 1.3 8.03 7.99 1.72 0.39 0 4.0 3.9 3.3 2.7 2.2 88.1 84.3 81.7 77.4 71.1 5.1 4.8 4.5 3.1 2.5 3.9 3.9 4.9 7.1 8.3 89.9 83.7 66.8 61.1 7.5 6.4 5.5 4.2 3.4 1.5 3.6 4.8 5.6 7.4 7.9 12.3 25.9 20.5 7.8 6.6 6.2 4.5 3.2 1.7 3.4 6.5 8.7 12.0 2.2 4.0 7.3 18.4 (continued on next page) 36.7 32.6 19.7 17.2 17.9 31.5 34.2 50.5 57.9 61.2 22.1 21.6 10.7 9.4 9.1 3.7 3.9 4.0 3.7 3.0 6.0 6.8 11.3 8.5 6.9 57.8 57.2 55.6 52.8 51.4 1.9 7.3 21.2 20.5 19.3 0 0.8 2.2 4.3 5.9 45.2 44.0 36.3 38.9 42.1 1.0 2.6 9.6 8.8 6.8 17.3 18.2 20.0 25.9 25.9 4.7 4.5 3.7 5.5 6.4 23.7 21.4 15.6 22.8 23.3 19.2 20.7 24.1 27.2 24.0 12.4 15.8 23.3 4.6 4.1 1.4 1.6 2.4 3.0 4.6 1.8 2.1 3.2 4.0 5.6 1.3 2.4 3.4 3.8 5.6 1.6 2.2 3.1 3.8 4.7 88.5 84.6 79.7 75.6 62.6 0.1 0.4 0.8 1.6 2.4 1.8 2.3 2.3 2.7 4.8 2.6 3.1 3.1 3.1 5.8 18.7 18.2 18.2 18.5 17.4 14.4 14.9 15.3 15.3 13.6 30.4 28.6 25.3 27.2 28.0 5.1 5.7 6.9 8.3 8.3 2.9 3.2 3.6 4.3 7.3 4.4 5.6 5.6 6.5 7.1 0.8 2.7 5.5 2.7 1.8 C6 C6Z CC6 C8 iC8 B T o-X ETB P MTBE

0.95

0.96

0.23

0.979

0.99

K0.09

2316 Table 1 (continued ) Pollutant, l 0.91 0.83 ETB 1.25 1.11 1 0.91 0.83 o-Xylene 1.25 1.11 1 0.91 0.83 iPB 1.25 1.11 1 0.91 0.83 Fuel component r2 a1 B1 C6

E. Zervas et al. / Fuel 83 (2004) 23132321

C6Z

CC6

C8

iC8

T 57.5

o-X 20.1 2.3 2.8 8.0 3.6 2.3 100 100 100 100 100

ETB 22.4 97.3 94.5 85.1 92.5 95.9

MTBE

0.980

0.98

0.09

0.4 2.7 6.9 3.9 1.8

0.980

0.96

K0.84

0.985

0.96

0.11

4.5 4.4 4.1 2.6 1.3

0 0 15 13 12

95.5 95.6 80.7 84.5 86.9

stoichiometry, the majority (71%) of exhaust 1-hexene comes from fuel 1-hexene, 27% from fuel cyclohexane, but a small quantity (2%) from fuel octane. The addition of hexane does not change this model. The percentage of 1-hexene increases at rich conditions, the one of cyclohexane remains almost constant, while the percentage of octane decreases from 8 to 0%. In the case of cyclohexane, a closer analysis shows that the addition of fuel aromatics improves this model for every l used. At stoichiometry, the majority (80%) of cyclohexane comes from fuel cyclohexane, but aromatics contribute with 36% each. The specic weight of cyclohexane increases at rich conditions, while this of aromatics at lean ones. According to the improved model, at stoichiometry, the 81% of exhaust iPB comes from fuel ETB; fuel o-xylene contributes by 15% and the rest 4% comes from fuel toluene. These percentages change with l; the specic weight of toluene is more important at lean conditions, the percentage of ETB presents a minimum value at lZ1.0, while o-xylene participates only at rich conditions. Benzene does not participate to this model. Pentane, hexane, octane, isooctane and o-xylene come only from the respective fuel components. The addition of other fuel components does not improve these correlations. The r2 of the lines Predicted valuesZa1!experimental valuesCb1 are 0.934, 0.979, 0.971, 0.978 and 0.980, respectively, for the above models, indicating a very good accordance between predicted and experimental values (the a1 are 0.923, 0.985, 0.951, 0.978 and 0.960 and the b1 are 0.038, 0.001, 0.202, 0.190 and K0.84, respectively).

3.2. Formation paths Methane is the lighter hydrocarbon and its formation is at the end of the cracking path of all the other HC. It is clearly enhanced by some hydrocarbons that obviously can produce more CH3 radicals than the others (for example o-xylene or isooctane), but normally it can be formed from all fuel components. The same conclusions are valuable in the case of ethane; even if it is clearly enhanced by some fuel components, it can be produced from many hydrocarbons by b-scissions. Ethylene. This pollutant is a product of b-scission of higher HC. Octane is the main source of ethylene, because it can easily proceed to its formation by three b-scissions (Fig. 6); hexane (Fig. 1) and 1-hexene (Fig. 2) can proceed by two. The contribution of cyclohexane is smaller because it must rstly proceed by a ring opening (Fig. 3). Isooctane can produce C2 products at the end of its combustion, but as this path is more difcult than the b-scissions of the above fuel components, its contribution is lower. ETB can give ethylene after a dealkylation of the ethyl radical [6], but the quantity of ethylene produced is smaller than this of the other sources. Other aromatics can produce this compound after a ring opening, formation of unsaturated C2 radicals and combination with H, but this path seems quite difcult. Acetylene. Zhang [11] studies the combustion of benzene and proposes that the formation of acetylene is found on the main path of its oxidation: C6H60C6H50C4H30C2H2. The other aromatics can also follow the same mechanism after a dealkylation. Acetylene can also be produced from

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Fig. 1. Proposed path for the hexane combustion and formation of ethylene, propylene and 1-butene.

all the other hydrocarbons by b-scissions followed by H extraction, but its formation after this mechanism, is more difcult than that of ethylene; this is the reason of its lower concentration comparing to ethylene.

Fig. 3. Proposed path for the cyclohexane combustion and formation of ethylene, propylene, 1,3-butadiene and 1-hexene.

Propylene: from 2-propanol (Fig. 4). This compound loses its OH and the corresponding radical is stabilized losing an H. From isooctane (Fig. 5). Isooctane can initially break in two points and form either two C4 radicals or a C3 and a C5 [12]. The C3 radical loses an H to form propylene. Another path is the formation of an tertiary isooctyl radical [13], which is decomposed to a methyl radical and propylene [14]. From 1-hexene (Fig. 2). 1-Hexene can initially give a C2 and a C4 radical but also two C3 ones. The primary C3 radical can give a secondary one by internal arrangements and propylene after an H extraction. The unsaturated C3 radical can combine with an H to form

Fig. 2. Proposed path for the 1-hexene combustion and formation of ethylene, propylene and 1-butene.

Fig. 4. Proposed path for the 2-propanol combustion and formation of propylene.

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Fig. 6. Proposed path for the octane combustion and formation of ethylene, propylene and 1-hexene.

Fig. 5. Proposed path for the isooctane combustion and formation of propylene, isobutene, isobutene and 1-butene.

propylene. The break into two C3 radicals must be less easy than this into a C2 and a C4, explaining the higher concentration of C2 products than this of propylene from the hexene fuel [8]. From hexane (Fig. 1). Hexane looses an H (preferably secondary [13]) to form a C6 radical which can give a C3 radical and a propylene. As previously, the rst radical can give propylene after an H extraction. As in the case of 1-hexene, hexane can preferably give a C2 and a C4 radical instead of two C3 ones [15], explaining the higher concentration of C2 products than propylene obtained from the hexane fuel. From cyclohexane (Fig. 3). Cyclohexane opens the ring and the C6 radical formed follows the mechanism described in the case of 1-hexene. As this mechanism has a supplementary stage, the participation of cyclohexane to the formation of propylene is lower than this of 1-hexene. From n-octane (Fig. 6). Octane gives preferably a C2 and a C6 radical after a b-scission. The C6 one can follow the previous mechanism to give propylene. This mechanism has one more stage for the formation of propylene than this of 1-hexane explaining the lower participation of octane than 1-hexene to the formation of this pollutant.

Isobutane. The formation paths of isobutane from isooctane are presented in literature ([16,17], Fig. 5). According to these articles, isooctane gives an isooctyl radical followed by two C4 parts. Both radicals can give an isobutane after combination with an H. This reaction takes place rather at the end of the reaction before the cooling phase; if oxidation continues, C4 radicals will give lighter products. Another path is the formation of a tertiary isooctyl radical [13], which is decomposed to isobutyl radical and isobutene following a b-scission. The isobutyl radical can give isobutene with a combination with H. The rst path can be applied in the case of MTBE (Fig. 7). 1-Butene: from n-octane (Fig. 6). n-Octane breaks in two C4 parts, a C4 radical and isobutene [18]. The rst C4 radical can also give a 1-butene after an H extraction [12]. From nhexane (Fig. 1). Hexane forms initially a secondary radical in position 2 or 3 [15]. The 3-hexyl radical gives 1-butene or a C4H7 radical that can give 1-butene after an H extraction, while the 2-hexyl breaks into two C3 products [19]. From 1-hexene (Fig. 2). 1-Hexene, looses an H in allylic position and forms the 3-hexenyl radical which is quite stable for resonance reasons [12,19]. This radical gives, by b-scission, a C4H7 radical that takes an H to form 1-butene, or looses an H to form 1,3-butadiene [12]. An attack of O or OH on the 1-hexene can directly give a C4H7 radical and an ethylene or a 1-butene and a C2H3 radical [19]. Another path is the addition of an H to 1-hexene to form a C6H13 that

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Fig. 7. Proposed path for the MTBE combustion and formation of isobutene, formaldehyde and methanol and probable formation of isobutane.

gives an ethylene and a primary C4H9 radical [19]. This last looses an H to form 1-butene [12]. From isooctane (Fig. 5). This path must be quite complex; isooctane gives initially an isooctyl radical that breaks, giving principally isobutene and an isobutyl radical [15]. A methyl radical must migrate before the formation of 1-butene. The complexity of this path explains the low contribution of isooctane to the formation of this pollutant. Isobutene: from isooctane (Fig. 5). Isooctane produces preferably an tertiary isooctyl radical, but it can also be a secondary or primary one [13]. The tertiary radical is decomposed to isobutyl radical and isobutene following a b-scission. The tertiobutyl radical is preferably decomposed to a methyl radical and propylene [14], but it can also give an isobutene or isobutane loosing or taking an H [12]. The secondary radical mainly gives a methyl and 2,4-dimethylpentene or 2,2-dimethylpentene [20]. The primary iC8 radical is decomposed in the same place as the tertiary giving the same products (isobutene and tertiobutyl); it can also give propylene and a neo-pentylene radical. This last is decomposed in methyl and isobutene [14]. At very high temperature, isooctane can give directly the tC4H9 and iC4H9 radicals, or neoC5H11 and iC3H7, which continue by the previous reactions [13]. From MTBE (Fig. 7). MTBE looses initially an H [14,21]. The CH bond of the methyl is weaker than this of tertiobutyl [22]. This radical breaks into two smaller pieces, a tertiobutyl radical and formaldehyde, or isobutene and a CH3O radical [22]. The (CH3)3C radical can give isobutene after an H extraction. Another path is the direct decomposition of MTBE to give isobutene and methanol [22].

Cis and trans-2-butene. Our results are not sufcient to propose a path for their formation. o-Xylene must break to two C4 radicals with a breaking point between the two methyls. These radicals must then react with H to form the cis or trans form of 2-butene. Butadiene: from cyclohexane (Fig 3). Cyclohexane looses an H to form a C6H11 radical, which opens to give a straight chain radical [23]. This last one can react with an H to form 1 hexene or break into two parts by a b-scission and form 1,3-butadiene [19,23]. From 1-hexene (Fig. 2). A direct attack of O or OH on the 1-hexene can give ethylene and a C4H7 radical [19]. This last one can loose an H and form 1,3-butadiene. Another probable path is the formation of a C6H11 after an H extraction, a b-scission and formation of 1,3-butadiene after an H extraction. Hexane does not produce 1,3-butadiene, because its initial radical is preferably secondary and it is decomposed by a b-scission to give smaller products. To obtain 1,3-butadiene from hexane, the following reaction must take place: formation of a primary radical, then formation of 1-hexene from this radical or directly from hexane, which must loose an H at the opposite side of the double bond and continue with the reactions presented previously. However, as hexane does not produce 1-hexene, this path does not take place. Isopentane. The formation mechanism of isopentane from isooctane must be based on the consecutive extraction of three methyl radicals from this fuel component and the combination with an H for the termination reactions, or the re-arrangement of an isopentyl radical. 1-Hexene. A part of exhaust 1-hexene comes from the unburned fuel; the rest comes from cyclohexane (Fig. 3) and n-octane (Fig. 6). As in the case of 1,3-butadiene, cyclohexane forms a C6 straight chain radical [23], which forms 1-hexene after a combination with an H. It must be noticed that hexane does not produce 1-hexene, because it forms preferentially secondary radicals, which are broken into smaller pieces. n-Octane gives a and a C6 radical after a b-scission. This radical gives 1-hexene after an H extraction [24]. Cyclohexane. The majority of cyclohexane comes from unburned fuel; its formation from aromatics proceeds by a dealkylation followed by a hydrogenation (Fig. 8). Benzene (Fig. 8). Fuel benzene gives the majority of exhaust benzene. Fuel aromatics proceed by a dealkylation; the benzyl radical formed is then combined with a hydrogen to give benzene. This reaction is more important at rich conditions due to the lack of oxygen. At lean ones, the intermediate products are further oxidized to CO. The detailed mechanism of benzenes formation from higher aromatics is presented in literature [20,25]. Benzene is formed from cyclohexane by the consequentially loss of three atoms of hydrogen. A double bond must be formed rst. Several mechanisms can produce it, as for example: oxidation to alcohol and abstraction of a molecule of water [25] or production of an alkyl radical by abstraction of a rst and then a second H [18]. Following these mechanisms, the second and the third double bond are then formed to give

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E. Zervas et al. / Fuel 83 (2004) 23132321

Fig. 8. Proposed path for the combustion of aromatics and formation of ethylene, cyclohexane, benzene, toluene, ETB, o-xylene and iPB.

benzene. The formation of benzene from cyclohexane is more important at rich than at lean conditions, but its specic weight is more important at lean ones. Another reaction for benzenes formation is the addition of propargyl radicals to allene [24]. As many fuel compounds can give these two radicals, benzene can be formed from almost every fuel. But, as the exhaust concentrations measured in the case of fuels without aromatics or cyclohexane are very low, this last reaction is very minor comparing to the direct formation from aromatics. The formation of benzene from isooctane follows probably this last path. Toluene (Fig. 8). The majority of exhaust toluene comes from the unburned fuel. Its formation from o-xylene follows an extraction of the methyl radical and a combination with an hydrogen to give toluene, or by the formation of intermediate oxygenated products. These detailed mechanisms are presented in literature [20]. ETB forms an initial radical in a position [25,26]. The next step can be: FCH2CH30FCH2CCH3, or FCH2CH30FCHCH3CH, or FCH2CH30FCCH2CH3. The enthalpies of these reactions are 306, 331 and 376 KJ/mole, respectively [27]. These data indicate that the most favorable path is the rst one; the combination of an H can then give toluene. In both cases, o-xylene and ETB, the formation of toluene needs

the combination of an H. This must be a termination reaction that takes place during the cooling phase. ETB (Fig. 8). A part of exhaust ETB comes from the unburned fuel. Toluene loses an H to form a F-CH2, which can react with a methyl to give ETB. o-Xylene loses rst a CH3; the formed radical must then give a F-CH2 by internal arrangements, which reacts with a methyl to give ETB. As during the combustion process, the reactions give generally smaller products, these last two reactions must take place during the cooling phase. o-Xylene (Fig. 8). Contrary to ETB, o-xylene is not coming from other fuel aromatics, but it is only a product of the unburned fuel. The only probable path to this formation could be the extraction of a hydrogen from the aromatic nucleus of toluene, and the addition of a methyl radical at this place. This mechanism is quite unlike to happen even during the cooling phase; this aromatic gives rather lower products. The same remarks are valuable in the case of ETB. Isopropylbenzene (Fig. 8). ETB rstly loses an H. The radical formed can follow two ways: the transformation to lower intermediate products (toluene, benzene), or the reaction with CH3 to form iPB. This reaction needs the formation of C6H5CHCH3, which is less enhanced than that of C6H5CH2 [25]; for this reason the principal product of ETB is toluene. The combination of a methyl radical probably takes place during the cooling phase. In the case of o-xylene, this one loses initially a CH3. This radical is then transformed to a F-CH2 by internal arrangements, as for the formation of ETB, and follows the second path of the previous reaction. Toluene loses initially a hydrogen to form the F-CH2 which follows also the previous reactions. The contribution of o-xylene is lower than this of ETB due to the more complicated path needed for the formation of iPB. Toluene gives less iPB because it gives preferably benzene or lower products. Pentane, hexane, octane and isooctane are products only of the unburned fuel.

4. Conclusions The previous article [8] work allowed the qualitative determination of the precursors of each exhaust specic hydrocarbon. This work allowed the quantitative determination of each precursor at stoichiometry, lean and rich conditions. Concerning the emissions of main exhaust hydrocarbons at stoichiometry: the majority of ethylene comes from fuel octane (25.3%), hexane (19.6%), 1-hexene (18.2%) and cyclohexane (15.3%), while the majority (80%) of acetylene comes from fuel benzene, the most important source of propylene at stoichiometry is fuel isooctane (24.1%), 2-propanol (23.3%), 1-hexene

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(20.0%), octane (15.6%), hexane (13.3%) and cyclohexane (3.7%), 1-butene is formed from fuel octane (36.3%), hexane (32.8%), hexene (21.2%) and isooctane (9.6%); most of the half (55.6%) of exhaust isobutene comes from fuel MTBE and the rest from isooctane; more than the half of exhaust 1,3-butadiene comes from fuel cyclohexane (50.5%); the other sources are 1-hexene (19.7%), oxylene (11.3%), octane (10.7%), isooctane (4.0%) and hexane (3.8%), isopentane is mainly produced by fuel isopentane, but small amounts (11.7%) come from fuel isooctane, the majority (71%) of exhaust 1-hexene comes from fuel 1-hexene, 27% from fuel cyclohexane, but a small quantity (2%) from fuel octane; the majority (80%) of exhaust cyclohexane comes from fuel cyclohexane, but aromatics contribute with 36% each? the majority (82%) of exhaust benzene comes from fuel benzene; the other sources are ETB, toluene, o-xylene and cyclohexane, the two-thirds of toluene come from fuel toluene, while fuel o-xylene contributes with 26% and the rest comes from fuel ETB; exhaust ETB is mainly (85%) produced from fuel ETB, while the rest comes from toluene and o-xylene; the majority (81%) of isopropylbenzene comes from fuel ETB; fuel o-xylene contributes by 15% and the rest 4% comes from fuel toluene, no model is found in the case of methane and ethane, because these HC have many precursors, not always related with the initial fuel composition, n-pentane, hexane, octane, isooctane and o-xylene come only from the respective fuel components, for each exhaust hydrocarbon, a detailed formation path is proposed.

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