J Braz. Soc. Mech. Sci. Eng.

(2014) 36:403–410
DOI 10.1007/s40430-013-0094-y

TECHNICAL PAPER

Combustion time of the oxygenated and non-oxygenated fuels

in an Otto cycle engine
Pedro Mello • Fabiano Wildner • Giovanni Souza de Andrade •

Renato Cataluña • Rosângela da Silva

Received: 14 January 2011 / Accepted: 4 November 2011 / Published online: 27 October 2013
Ó The Author(s) 2013. This article is published with open access at Springerlink.com

Abstract Speed flame propagation in Otto cycle engines compression ratios measured as compared to the non-
is one of the principal characteristics of fuel and is fun- oxygenated (isooctane) and oxygenated fuels (MTBE and
damental in defining the ignition advance. The greater the TAEE).
propagation speed the less the negative work required to
compress the mixture before the piston reaches the top Keywords Fuels
Speed flame propagation
Otto
dead center and the higher the cycle’s efficiency. This cycle engine
paper presents experimental results of time measurements
of the fuel’s ignition and the maximum pressure rating in List of symbols
the combustion chamber of a Cooperative Fuel Research AKI Antiknock Index ([(MON ? RON)/2])
engine specially instrumented. The combustion duration Hz Hertz frequency unit is derived from the International
measurements of oxygenated and non-oxygenated fuels System (IS) for frequency, which is expressed in
were taken as a function of the compression ratio (8:1, 10:1 terms of cycles per second
and 12:1) and lambda (k). The speed flame propagation in Kpa 103 Pa (Pascal) unidade padrão Multiple of the
the combustion chamber is significantly changed with the standard unit of pressure and tension of the
change of the lambda different compression ratios. The International System (IS)
VNG has a maximum in the speed flame propagation in the k lambda expresses a relationship between the mass
stoichiometric region (k = 1.0) in all compression rates in of air and fuel admitted to in a given instant by the
this study. Similar behavior occurs with ethanol and gas- engine, compared to the masses of air and fuel
ohol, but only in compression ratio 12:1. Ethanol and chemically balanced
gasohol have the higher rate of flame propagation for all

1 Introduction
Technical Editor: Demetrio Neto.
In conventional spark-ignition engines, the fuel and air pass
P. Mello (&)
F. Wildner
G. S. de Andrade
through intake manifold into the cylinder’s, where they are
Department of Mechanical Engineering, Federal University of
Rio Grande do Sul, Porto Alegre, RS 90050170, Brazil mixed with the residual gas and then compressed. Under
e-mail: [email protected] normal operating conditions, combustion is triggered by an
F. Wildner electric discharge during compression. The flame front
e-mail: [email protected] propagates through the air–fuel mixture until it reaches the
walls of the combustion chamber, where it is extinguished.
R. Cataluña
R. da Silva
At the onset of combustion caused by the spark from the
Department of Physical Chemistry, Federal University of Rio
Grande do Sul, Porto Alegre, RS 90050170, Brazil spark-plug, the speed flame propagation is small and is
e-mail: [email protected] accompanied by a slight increase in pressure (delay time)
R. da Silva due to combustion. The flame front increases progressively
e-mail: [email protected] and propagates through the combustion chamber until the

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404 J Braz. Soc. Mech. Sci. Eng. (2014) 36:403–410

pressure inside the cylinder reaches its maximum after the for an operating condition [4]. The engine’s geometric
top dead center (TDC). parameters affect the turbulence and surface area of the
The combustion process is divided into four distinct flame front. Aerodynamic details of the intake system
phases: ignition, development, propagation and end of contribute to the creation of an oriented gas flow, changing
flame. The maximum combustion pressure must occur at a the flame’s surface area and path. The shape of the com-
point (15° after TDC) that provides the maximum power or bustion chamber also affects other criteria such as volu-
maximum torque. Combustion starts immediately after metric efficiency, knocking trend and pollutant emissions.
spark ignition, but, because the initial stages are quite slow, Combustion speed measurements in a laminar system using
the ignition delay period is used to describe the first stage. pure hydrocarbons indicated that, for the same air–fuel
Second Ishii et al. [1] it is difficult precisely determine the ratio, the speed flame varies as a function of the fuel’s
end of combustion because of burning late phenomenon [2]. chemical structure [9, 18, 19].
For these reasons, ignition delay and end of combustion are Due to the constant increase in crude oil-derived liquid
usually defined arbitrarily. Ignition delay can, for example, fuel prices and the growing restrictions with respect to
be considered the time period in which the ratio of burned environmental contamination, interest has focused
gas reaches a value of 5 [3] or 10 % [4]; [5] and end of increasingly on alternative fuels [20–27]. These fuels can
combustion as the time period in which this ratio reaches the be classified as synthetic gasoline, gasoline with oxygen-
value of 85 [4, 6] or 90 % [3]. If the onset of combustion ated compound additives such as methyl tert-butyl ether
advances progressively before the TDC, the negative work (MTBE), tert-amyl-ethyl-ether (TAEE) [28, 29]. Studies of
of compression increases. If ignition is delayed, the pressure the speed flame propagation of new oxygenated fuels such
peak occurs later and its value is reduced. The appropriate as TAEE are important to determine the best ignition
time for the onset of the combustion process depends on the advance to reach the maximum brake torque. This paper
speed flame propagation and on the geometric configuration analyzes the variation in burning speed of a Brazilian
of the combustion chamber. These depend on the engine commercial gasoline (gasohol), isooctane, MTBE, TAEE,
design, the operating conditions and the properties of the ethanol and vehicular natural gas (VNG) at different
fuel–air mixture [7–9, 4]. compression ratios and air–fuel ratios. Compression ratios
Complete combustion is described as that in which the used in this study were 8:1, 10:1, and 12:1 for the liquid
flame front moves through the combustion chamber until fuels and 14:1 for VNG. The air–fuel ratios used for each
the air–fuel mixture is completely consumed and trans- compression ratio were 0.8 and 0.9 (rich mixture), 1.0
formed into carbon dioxide and water. During the com- (stoichiometric), and 1.1 and 1.2 (lean conditions).
bustion process, carbon monoxide, unburned hydrocarbons
and nitrogen oxide are present due to kinetic effects. Factors
such as the fuel’s composition, air–fuel ratio, geometric 2 Materials and methods
details, temperature, pressure, compression ratio and
deposits in the chamber determine the physical and chem- Six different fuels were used in this study: a Brazilian
ical characteristics of the combustion process [10–13]. The commercial gasoline (gasohol), isooctane 99 %, MTBE
reactions that occur during the combustion process are 99 %, TAEE 99 %, ethanol 99.3 % and VNG. The VNG
determined by serial and parallel mechanisms whose stages contained 89 % methane, 7 % ethane and 2 % propane.
initiate in response to the formation of radicals and reac- Table 1 lists the physicochemical characteristics of the
tions due to equilibrium displacement. In many cases, due liquid fuels used here.
to the high release of energy and the resulting increase in According to table, ethanol shows a higher antiknock
temperature, the speed of the reaction increases exponen- index (AKI) than the ramified ethers (TAEE and MTBE)
tially, leading to possible detonation or knocking [4]. and isooctane. The antiknocking strength is an extremely
Knocking depends on the temperature, the system’s pres- important property of fuel for Otto cycle engines, since it
sure, and the fuel’s physicochemical characteristics [9]. At should not auto ignition by compression, but by sparking.
very low pressures, the system is outside the knock region Combustibles having a high octane index produce a milder
and the mixture reacts mildly [4, 14–16]. and more effective combustion. The octane number is
In engines with optimal design, the turbulence inside the simply a numerical description of its resistance to auto
combustion chamber is proportional to the engine’s revo- ignition without entering into a knocking process (sponta-
lution and increases the speed flame propagation [4, 17]. neous burning of the mixture). The average of the Motor
High revolution requires a great advance in the ignition, Octane Number (MON) (ASTM D 2700-97) [30] and
because the spark time for a given mass of fuel and air Research Octane Number (RON) (ASTM D 2699-97) [31]
inside the cylinder is set to give the maximum brake torque is known as the Antiknock, AKI = [(MON ? RON)/2].

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J Braz. Soc. Mech. Sci. Eng. (2014) 36:403–410 405

Table 1 Physicochemical characteristics of the liquid fuels used in this study {Fonte: [10, 29]}
Physicochemical characteristics Gasohol Isooctane Ethanol TAEE* MTBE

Reid vapor pressure (kPa) 69 11 16 13 54

Distillation range (°C) 35–201 99 78 102 55
Antiknock index (AKI) 87 100 115 108 109
-3
Density (g cm ) 20/20 °C 0.740 0.692 0.792 0.767 0.742

Volatility can be understood as the ease with which fuel 220

Evaporate Temperature (°C)

evaporates. This property is extremely important since the
180
combustion process takes in a gaseous environment, i.e.,
inside the engine, where the fuel must first vaporize so that 140
combustion can occur. The volatility is determined based
on the properties of Reid vapor pressure and distillation 100
curve.
Fuels with high vapor pressure present high rate emis- 60
sion of volatile organic compounds (VOCs). However,
there is a minimum required for starting at low tempera- 20
0 20 40 60 80 100
tures. Fuels with low vapor pressures and high enthalpy of % Evaporate
vaporization have trouble in completing vaporization in the
intake manifold, making the combustion process and Fig. 1 Distillation profile of gasohol
reducing engine performance. The higher the enthalpy of
vaporization the smaller is the resulting temperature in the exerted by the vapors of the same confined space (the force
intake manifold, increasing the volumetric efficiency of the per unit area exerted on the liquid surface). For pure
plunger. There is currently a strong trend in reducing the hydrocarbon, steam pressure depends on the temperature
volatility of parameters, among these the vapor pressure in and enthalpy of vaporization. For gasoline, which are
gasoline [32–35]. The behavior of the vehicle with respect mixtures of hydrocarbons, depends on the relative con-
to the volatility of gasoline at low temperatures can cause centrations and the interaction of the constituents of the
incomplete fuel vaporization and in an uncontrolled air/fuel mixture [35].
ratio. Considerable progress has occurred in this area, such Figure 1 shows the profile gasohol. The distillation
as replacing the carburetor injection system multipoint [9]. curve gives an idea of the volatility of gasoline throughout
The volatility parameters that have an effect on perfor- the range of distillation. The distillation curve can, in
mance at low temperature have been determined by testing simple terms, be represented by three points: T10, T50 and
vehicles at high speeds. At high temperatures, the most T90, which represent the temperatures at which 10, 50 and
common phenomena affecting fuel systems in vehicles are 90 % vaporization of de gasoline’s initial volume occurs
mainly steam ‘‘lock’’ and percolation. Vapor ‘‘lock’’ is the (ASTM D-86) [36–37]. These temperatures characterize
occurrence of a stock vaporized fuel from the fuel tank and the volatility of the fuel’s light, medium and heavy frac-
the carburetor or fuel injection system. Percolation is the tions. These fractions, in turn, affect the engine’s different
result of an uncontrolled vaporization of fuel, which can operating regimes. It should also be remembered that the
happen when the vehicle stops after a long period at high control of one or more properties of gasoline results in
operating temperatures. The enthalpy of vaporization has a proper combustion in car engines, and emissions of nitro-
strong influence on engine power because the higher the gen oxides (NOx), carbon monoxide (CO) and unburned
value, the greater the amount of heat removed from the hydrocarbons (HCs) may be reduced. The ideal fuel for
intake manifold and thereby lower the temperature of the reducing contaminants must have a Reid vapor pressure not
mixture allowed. This lowering of the temperature in the greater than 51.68 kPa, essentially zero olefins in its
combustion chamber increases the density of the air/fuel composition and temperature for the 50 % distillation point
mixture and with it, the mass of fuel to be oxidized is (ASTM D-86) [36] greater than 82 °C but \96.1 °C. The
increased, favoring an increase of engine power. In general, profile abnormal distillation gasohol is due to azeotrope
the vapor pressure of a volatile liquid is the pressure formed by ethanol and hydrocarbons, wherein the

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406 J Braz. Soc. Mech. Sci. Eng. (2014) 36:403–410

composition volumetric gasohol consisted of 13 % normal cylinder equipped with a pressure control valve and the
paraffins, 23 % isoparaffins, 13 % naphthenes, 11 % ole- dosing was done with a mixer mounted on the intake
fins, 9 % aromatics and ethanol 25 %. manifold of the CFR engine. The engine’s original system,
When considering the flow of the fuel through a car- which was used for the other fuels, consisted of a triple
buretor jet, the coefficient of discharge for normal hydro- barrel carburetor with adjustable height for adjustment of
carbon fuels is virtually constant above a critical value of the air–fuel ratio.
the Reynolds number. Under these conditions, the mass The speed flame was obtained using a D-1 knock sensor
flow is a function of the density of the fuel so that increases (a standard component of the CFR engine). The D-1 sensor
mass flow and lowers the air–fuel ratio of the mixture. This has a stainless steel diaphragm, which induces a voltage in
is partly offset by the lower level in the float chamber that the sensor through the action of pressure. The induced
occurs with heavier fuels. There is such compensating voltage signal is proportional to the pressure rate in the
factor with injection vehicles where the mass of fuel combustion chamber. In this work, speed flame propaga-
injected will depend directly on the density of the fuel. tion was defined as the angle between the spark ignition
Variations in density between commercial fuels will and the maximum pressure rate inside the combustion
therefore influence the air/fuel ratio unless there is an chamber divided by time. According Ishii et al. [1], the
engine management system to hold it at the optimum level. angle considered in flame propagation includes the ignition
Most gasolines have a density between about 0.72 and delay [4] and the maximum pressure rate. The ignition
0.78. The density will depend on the types of components advance was set at 10° to compare the speed flame prop-
used in blending the gasoline, aromatics compounds have agation of the fuels under study. The ignition was deter-
the highest density, with the olefins being intermediate and mined from the signal voltage of the electronic ignition
the paraffins having the lowest density, when compounds control system. The piston’s position was determined by a
having the same number of carbon atoms are compared. Of 600 mm diameter toothed wheel with 304 straight teeth
the pure compounds used in this study, ethanol has the and one slanted in the position relative to the top dead
highest density value. The tests to measure the speed flame center with the aid of an inductive sensor.
propagation were performed with a CFR engine (a Coop- The parameter (k) lambda expresses a relationship
erative Fuel Research engine (year 1951) manufactured by between the mass of air and fuel admitted to in a given
the Waukesha Engine Division) modified with an Otto instant by the engine, compared to the masses of air and
cycle cylinder head being specially instrumented with fuel chemically balanced. It is called ‘‘rich mixture’’
sensors and temperature indicators, D-1 Knock sensor, (k \ 1) when there is a lack of oxygen for the complete
Lambda probe, acquisition board, as shown in Fig. 2 a oxidation of all the reagent available in the combustion
schematic diagram of the system with the instrumentation chamber and is called ‘‘lean’’ (k [ 1) when there is excess
used in the tests. The VNG was stored in a high-pressure oxygen to the oxidation of all the available reagent into the

Fig. 2 Schematic diagram of the instrumentation system used in the tests

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J Braz. Soc. Mech. Sci. Eng. (2014) 36:403–410 407

320 CR 8:1

Speed flame propagation (t-1 s)

280

240

200 Ethanol

VNG
160
Gasohol

MTBE
120 Isooctane
TAEE

0,8 0,9 1,0 1,1 1,2

Lambda

CR 10:1
320

Speed flame propagation (t-1 s)

280

240 Ethanol

200 VNG
Isooctane
Gasohol
160 MTBE
TAEE

Fig. 3 Characteristic profiles of the signals from the position,

120
pressure variation and ignition sensors as a function of acquisition
time 0,8 0,9 1,0 1,1 1,2
Lambda
combustion chamber. The air–fuel ratio was adjusted using
a Bosch model LSU4 broadband lambda probe with a CR 12:1
MoTec PLM converter. The recorded pressure rate, posi- 320
Speed flame propagation (t-1 s)

tion and ignition sensor signals were obtained using a CIO

EXP GP and CIO DAS 16/330 data acquisition system at a 280
sampling rate of 55 kHz. Ethanol

240 Gasohol
The burning time in the combustion chamber was
Isooctane
defined as the interval between ignition and the maximum VNG
pressure variation inside the combustion chamber. The 200 MTBE

dimension of combustion duration was expressed as s-1, TAEE

160
and the tests were performed at a fixed revolution of
600 rpm (10 Hz). The ‘‘burn time’’ value of each fuel 120
under the different conditions analyzed here is the mean
value of 45 consecutive cycles after complete stabilization 0,8 0,9 1,0 1,1 1,2

of the operational conditions. After all the operational Lambda

conditions in the tests were stabilized, a comparison was Fig. 4 Speed measurement flame propagation tests under turbulent
made of the results. Figure 3 depicts the characteristic conditions for fuel this study as a function of the air–fuel ratio (k) and
profiles of the pressure rate, position and ignition sensors compression ratio 8:1, 10:1 and 12:1
signals recorded for the engine test, using gasohol as fuel
and a compression ratio of 8:1.
and the compression ratio can also be adjusted to achieve
3 Results and discussion maximum torque as a function of revolution and air–fuel
ratio.
The combustion speed flame is an important factor to The results presented in Table 1 indicate that the oxy-
adjust the best ignition advance. The cylinder’s dimension genated compounds showed the highest densities and

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408 J Braz. Soc. Mech. Sci. Eng. (2014) 36:403–410

antiknock index. The oxygenated compound TAEE pre- higher diffusion of mass and energy when density is high
sented the lowest vapor pressure. [38–39].
Figure 4 shows the results of the speed flame propaga- Note that among the rich mixtures (k = 0.8), fuels such
tion of fuels used in this study in function of the lambda in as ethers (MTBE and TAEE), gasohol and isooctane
different compression ratios (8:1, 10:1 and 12:1). present similar speed flame propagation. Among the oxy-
It is observed that the speed flame propagation in the genated compounds, ethanol presents the highest speed
combustion chamber is significantly changed with the flame propagation and among the hydrocarbons, VNG
change of the lambda to different compression rates. The shows the lowest flame speed with rich mixtures, which
VNG has a maximum in speed flame propagation in the increases with lean mixtures. Methane has high activation
region stoichiometric (k = 1.0) in all compression rates in energy in the oxidation process, which may explain the
this study. Similar behavior occurs with ethanol and gas- lower speed flame propagation observed at air–fuel ratios
ohol, but only in compression ratio 12:1. below the stoichiometric condition when the combustion
Evaluating rich region (k = 0.8 and 0.9) shows that the temperature is low. The best ignition advance for VNG
fuel reached the lowest flame propagation rate is VNG, should be higher than that of gasohol and oxygenated fuels
while the lean region (k = 1.1 and 1.2) the TAEE begins to to achieve maximum torque. Ethanol has higher speed
show a slower flame propagation in all compression ratios flame propagation, while the high flame speed of gasohol
studied. MTBE presents a behavior similar to TAEE to the can be attributed of the ethanol in its formulation. As
lean region can be explained of the oxygenated fuel TAEE, mentioned by Lawes et al. [40], the speed flame propaga-
whose molecular structure is similar to that of MTBE but tion of ethanol can be explained by the formation of
with a higher molecular weight. intermediate species such as acetaldehyde and formalde-
Ethanol and gasohol have the higher flame propagation hyde, whose high reactivity favors the oxidation process
rate for all compression ratios measured as compared to the [41–42].
non-oxygenated (Isooctane) and oxygenated fuels (MTBE The speed flame propagation of all the fuels analyzed,
and TAEE). Ethanol has a vapor pressure of about 16 kPa, except for VNG, here increases when the air–fuel ratio is
according to Table 1, however, when mixed with gasoline, rich and close to the stoichiometric ratio. This behavior can
form azeotropes with the hydrocarbons of minimum, which be explained by the fact that the combustion temperature
have a boiling point lower than that of two separate com- increases when it approaches the stoichiometric ratio.
ponents. This effect results in an increase of the vapor When the air–fuel ratio is above the stoichiometric ratio
pressure of the mixture. (lean mixture), the speed flame propagation diminishes in
Gasohol is a complex mixture of hydrocarbons and response to the decrease in combustion temperature caused
ethanol and it is impossible to attribute the increase or by excess air.
decrease to any specific compound. However, it is known
that linear chain compounds and olefins have a higher
combustion speed than branched and saturated compounds. 4 Conclusions
However, oxygenated compounds such as MTBE and
TAEE presented lower speed flame propagation than gas- The proper determination of the compression ratio and
oline, although ethanol showed values close to that of ignition advance for the optimal performance of engines is
Brazilian commercial fuel, whose composition contains directly related with the type of fuel employed. Fuels with
about 25 % v/v of ethanol. branched-chain and ether compounds show low speed
Higher burning speed requires smaller advancements. flame propagation. The speed flame propagation of ethanol
Fuels with low flame speed need a higher ignition advance is higher than that of branched-chain and ether compounds.
to maximize the torque. For VNG and gasohol, when used The use of compression ratio 12:1 increases the combus-
compression ratio 12, the highest combustion speed occurs tion speed of isooctane, VNG, TAEE, ethanol and gasohol
in the stoichiometric mixture condition, while the burning as compared with compression ratios 8:1 and 10:1. The
speed of oxygenated fuels is higher when the mixture is higher the compression ratio the greater is the speed flame
rich (k = 0.8–0.9) and diminishes when the mixture is lean propagation. To achieve high thermodynamic and
(k = 1.1–1.2), showing the profile for all compression ratio mechanical performance, internal combustion engines with
used in this study. For air–fuel ratios above the stoichi- spark ignition should operate with high compression rates,
ometric ratio (lean mixture), the combustion process and to minimize the negative work of compression, the
becomes unstable, leading to failures in the combustion ignition advance should be reduced to obtain the maximum
cycle. brake torque. The combustion speed diminishes at air–fuel
It should be noted that, as the compression ratio ratios above the stoichiometric ratio. The VNG has a
increases, so does the speed flame propagation, due to the maximum in the speed flame propagation in the

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J Braz. Soc. Mech. Sci. Eng. (2014) 36:403–410 409

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