10.5.

IGNITION DELAY
10.5.1. Definition and Discussion
The ignition delay in a diesel engine is defined as the time (or crank angle) interval between the start of injection and the start
of combustion. The SOI is usually taken as the time when the injector needle lifts off its seat. The SOC is more difficult to
determine precisely. It is often identified from the change in slope of the heat-release rate (from negative to positive)
calculated from the cylinder pressure data using the techniques described in Sec. 10.3.3. This occurs shortly after detectible
heat (chemical energy) release begins, which offsets the slight decline in cylinder pressure due to fuel evaporation within the
developing spray. However, hydrocarbon reaction chemistry is apparent within the spray before this point, evidenced by the
onset of luminosity (chemiluminescence). This luminosity effectively defines the onset of the breakup of the fuel molecules
and the initiation of partial fuel oxidation, and precedes the point of pressure rise by some 100 μs, about 1 crank-angle
degree.

Both physical and chemical processes must take place before a noticeable fraction of the chemical energy of the injected
liquid fuel can be released. The physical processes are: the atomization of the liquid fuel into droplets close to the injection
nozzle exit; the vaporization of some of these fuel droplets; the mixing of fuel vapor with air that has been entrained into the
spray. The chemical processes are the pre-major-heat-releasing combustion reactions of the fuel, air, residual gas mixture,
that lead to autoignition. These processes are affected by engine design and operating variables, and fuel characteristics, as
this section (10.5) examines.

Good atomization requires high fuel-injection pressure, small injector hole diameters, appropriate fuel viscosity, and high
cylinder air pressure at the time of injection (see Sec. 10.4.3). The rate of vaporization of the fuel droplets depends on the size
of the droplets, their distribution, and their velocity, the pressure and temperature inside the combustion chamber, and the
volatility of the fuel. The rate of fuel-air mixing is controlled largely by injector and combustion chamber design. Some
cylinder-head and piston-crown shapes are designed to amplify swirl and create turbulence in the air charge during
compression. IDI engine designs use a prechamber or swirl chamber to create the vigorous air motion necessary for rapid
fuel-air mixing. In DI engines, injector design features such as the number and spatial arrangement of the injector holes
determine the injected fuel distribution. The details of each nozzle hole affect the spray cone angle. The penetration of the
spray depends on the size of the fuel droplets, the injection pressure, the air density, and the air-flow characteristics. The
arrangement of the sprays, the spray cone angle, the extent of spray penetration, and the airflow all affect the rate of air
entrainment into the spray. These physical aspects of fuel-injection and fuel-spray behavior are reviewed in Sec. 10.4.

The chemical component of the ignition delay is controlled by the precombustion reactions of the fuel. A fundamental
discussion of autoignition or spontaneous hydrocarbon oxidation in premixed fuel-air mixtures is given in Sec. 9.6.2. Since the
diesel engine combustion process is heterogeneous, its spontaneous ignition process is especially complex. Ignition occurs in
regions where fuel vapor has mixed with some air, through the cracking of large hydrocarbon molecules to smaller molecules
(partial oxidation reactions). These chemical processes depend on the composition of the fuel and the cylinder charge
temperature and pressure, as well as the physical processes described above which govern the distribution of fuel within each
spray.

Since the spontaneous ignition characteristics of the fuel affect the ignition delay, this property of a fuel is very important in
determining diesel engine operating characteristics such as fuel conversion efficiency, smoothness of operation, misfire,
smoke emissions, noise, and ease of starting. The ignition quality of a fuel is defined by its cetane number. Cetane number is
determined by comparing the ignition delay of the fuel with that of primary reference fuel mixtures in a standardized engine
test (see Sec. 10.5.2). For low cetane fuels with too long an ignition delay, most of the fuel will be injected before ignition
occurs, which results in very rapid burning rates once combustion starts with high rates of pressure rise and high peak
pressures. Under extreme conditions, when the autoignition of much of the injected fuel occurs after a long delay (e.g., under

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cold-starting conditions), this produces an audible "knocking sound," often referred to as diesel knock. For higher cetane
number fuels, with shorter ignition delays, ignition occurs before most of the fuel has been injected. The rates of heat release
and pressure rise are then controlled primarily by the rate of injection and fuel-air mixing, and smoother engine operation
results.

The timing relationships between the various measures of autoignition onset and the fuel injection process, as a function of
the in-cylinder air temperature at SOI (close to TC), are shown in Fig. 10.41. (Note that 1 ms at 1800 rev/min corresponds to
about 10 crank-angle degrees.) Typical end-of-compression temperatures in a warmed-up engine are close to 1000 K. The
luminosity onset precedes the pressure recovery point at 1000 K by about 0.2 ms (about 2 degrees CA). Under cold-start
conditions (750 to 800 K air temperature), the pressure rise lag is significantly longer. The mixture temperature values where
the autoignition chemistry transitions from low- to intermediate- to high-temperature reaction schemes are indicated:33
Section 10.5.3 will further discuss these details.

Figure 10.41 Timing of several fundamental features of the diesel spray autoignition process as a
function of in-cylinder air temperature at time of injection. Symbols show measured times (in a
constant volume combustion vessel) of luminosity onset and pressure recovery (rise) occurrence.
Solid lines show approximate times for the spray to impinge on the chamber walls, and of end of
injection. Ignition did not occur for gas temperatures below about 750 K.33

Pilot injection (the injection of 5 to 10% of the fuel some 10 to 20 degrees before the start of the main injection) is a strategy
enabled by the development of multi-pulse fuel injection technology (see Sec. 10.7.1) that is used to shorten the ignition
delay. The spontaneous ignition and combustion of the pilot fuel creates a hotter local gas environment around the fuel
injector into which the main injection sprays penetrate. The higher temperature of the ambient gas (mainly air), which is then
entrained into the main-injection sprays, raises the within-the-spray mixture temperature thus speeding up the premixed-
mixture ignition chemistry.

10.5.2. Fuel Ignition Quality

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The ignition quality of a diesel fuel is defined by its cetane number. The method used to determine the ignition quality in terms
of cetane number is analogous to that used for determining the antiknock quality of gasoline in terms of octane number. The
cetane number scale is defined by blends of two pure hydrocarbon reference fuels. Cetane (n-hexadecane, C16H34), a
hydrocarbon with high ignition quality, represents the top of the scale with a cetane number of 100. An iso-cetane, 2-2-4-4-6-
8-8 heptamethyl-nonane (HMN), also C16H34, which has a very low ignition quality, represents the bottom of the scale with a
cetane number of 15.[1] Thus, cetane number (CN) is given by

CN = percent n-cetane + 0.15 × percent HMN

(10.31)

The engine used in cetane number determination is a standardized single-cylinder, variable compression ratio, engine with
special loading and accessory equipment and instrumentation. The engine, the operating conditions, and the test procedure
are specified by ASTM Method D 613. 34 The operating requirements include: engine speed, 900 rev/min; coolant temperature,
100°C; intake air temperature, 65.6°C (150°F); injection timing, 13° BTC; injection pressure, 10.3 MPa (1500 lb/in. 2). With the
engine operating under these conditions, on the fuel whose cetane number is to be determined, the compression ratio is
varied until combustion starts at TC: that is, an ignition delay period of 13° (2.4 ms at 900 rev/min) is produced. The above
procedure is then repeated using reference fuel blends. Each time a reference fuel is tried, the compression ratio is adjusted
to give the same 13° ignition delay. When the compression ratio required by the actual fuel is bracketed by the values required
by two reference fuel blends differing by less than five cetane numbers, the cetane number of the fuel is determined by
interpolation between the compression ratios required by the two reference blends.

Because of the expense of the cetane number test, many correlations which predict ignition quality based on the physical
properties of diesel fuels have been developed. A calculated cetane index (CCI) is often used to estimate ignition quality of
diesel fuels (ASTM D97635). It is based on API gravity and the mid-boiling point (temperature 50% evaporated). It is applicable
to straight-run fuels, catalytically cracked stocks, and blends of the two. Its use is suitable for most diesel fuels and gives
numbers that correspond quite closely to cetane number. A diesel index is also used. It is based on the fact that ignition
quality is linked to hydrocarbon composition: n-paraffins have high ignition quality, and aromatic and napthenic compounds
have low ignition quality. The aniline point (ASTM D61136), the lowest temperature at which equal volumes of the fuel and
aniline become just miscible, is used together with the API gravity to give the diesel index:[2]

Diesel index = aniline point (°F) × API gravity /100

j

(10.32)

The diesel index depends on the fact that aromatic hydrocarbons mix completely with aniline at comparatively low
temperatures, whereas paraffins require considerably higher temperatures before they are completely miscible. Similarly, a
high API gravity denotes low specific gravity and high paraffinicity and, again, good ignition quality. The diesel index usually
gives values slightly above the cetane number. It provides a reasonable indication of ignition quality in many (but not all)
cases.

10.5.3. Autoignition and Premixed Burn

Basic studies in constant-volume combustion vessels, in steady-flow reactors, and in rapid-compression machines have been
used to examine the various stages by which autoignition of fuel-air mixtures under conditions relevant to diesel engines
occurs. In some of these studies the fuel and air were premixed; in many, fuel injection was used. Studies with fuel injection
into constant-temperature and pressure environments, similar to conditions in a diesel engine at TC of compression, have
identified the key steps in the process. The start of the diesel combustion process—spontaneous autoignition, followed by a

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short and rapid "premixed-burning" process—is illustrated by the natural flame emissions images in Fig. 10.42 with the
diagram showing the fuel injection profile (injector needle lift), apparent heat release rate and the cylinder pressure versus
crank angle.37 Faint (low intensity) chemiluminescence emission is apparent at 3.5° after start of injection (ASI), from the
early injected fuel vapor/entrained air mixture in the leading region of these eight fuel sprays. These regions are beyond the
"liquid length," the maximum penetration of the liquid fuel containing spray core (see Sec. 10.4.6). This chemiluminescence
(emitted because fuel molecule breakdown and partial oxidation is occurring) becomes much stronger (4.0° ASI and 4.5° ASI)
and clearly visible throughout the downstream region of all the sprays. Note that the apparent heat release rate is now rising
sharply: the premixed burn is getting underway.

Figure 10.42 Sequence of natural flame emissions images taken through a window in the piston
crown of an optical-access DI diesel engine with eight fuel sprays and 140-mm bore, operating at
naturally-aspirated engine conditions and 1200 rev/min. Timing of each image, after start of
injection (ASI), and relative light intensity gain (upper right of each image) are indicated. Bottom of
figure: apparent heat-release rate, cylinder pressure, injector needle lift profiles versus crank
angle.37

The early stages of the (weaker) chemiluminescence are primarily the result of contributions from formaldehyde (CH2O) and
CH emissions [see reactions in Eq. (9.63), an outline of the hydrocarbon autoignition chemistry], corresponding to the "cool-
flame" and "preignition glow" phenomena in rich mixtures. And the leading regions of these diesel sprays contain relatively
well-mixed rich fuel-vapor/entrained air mixture in the fuel-air equivalence ratio range of 2 to 4.37, 38

The hydrocarbons autoignition initiating mechanism is similar to the chemistry that initiates spark-ignition engine knock (see
Sec. 9.6.2). At sufficiently high temperatures, a hydrocarbon air mixture undergoes a sequence or chain of reactions that
produces an ever increasing pool of radicals (highly reactive species) through radical chain propagating and branching
reactions. As the bonds in the basic hydrocarbon molecule are successively broken, chemical energy is released at a first

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slowly then rapidly increasing rate. Radical removing (chain-terminating) reactions also occur, offsetting the radical build-up
to varying extent as chemistry and energy release proceed. See the reaction set in Eq. (9.63) which further delineates this
process.

The much brighter emission images in Fig. 10.42 (from about 5° to 6° ASI) result from soot particle radiation. Fuel molecule
breakdown in the rich fuel-vapor/air mixture within the spray, in the early chemiluminescence phase, leads to the formation of
PAHs which are precursors in the soot formation process (see Secs. 11.5.3 and 11.5.4 on diesel particulate formation). These
PAHs form rapidly, grow into nuclei, and grow and agglomerate into soot (primarily carbon) particles. Significant chemical
energy (heat) release is now occurring (6° ASI, Fig. 10.42).

The final images, 6.5° and 7° ASI, in Fig. 10.42 show the development of diffusion flames around the individual sprays. These
diffusion flames, where oxidation of the fuel is completed, are located at the spray boundaries with "fuel" (very rich mixture
consisting of fuel vapor, partially reacted fuel molecules, PAHs, soot particles, CO, and H2) on the inside of the flame and air
on the outside, constitute the second mixing-controlled phase of diesel combustion where the majority of the heat release
occurs. By extrapolating the rounded portion of the heat release rate curve (which is this second mixing-controlled phase) at
its left-hand end down to the horizontal axis, one sees that these diffusion flames should become apparent at 6° to 6.5° ASI.
Note that these developing burning-spray images correspond to the illustrative schematic already shown in Fig. 10.11.
Autoignition usually commences a few crank-angle degrees after start of fuel injection, close to TC, in the rich fuel-
vapor/entrained-air mixture in the leading region of each developing spray, begins with the breakdown of fuel molecules
through high-enough velocity molecular collisions to initiate this bond-breaking process. It then continues and transitions into
the (rapid) premixed burning phase as the fuel hydrocarbon fragments build-up into PAHs, which continue to grow in
molecular size into soot particles releasing significant chemical energy in the process and increasing the temperature within
each spray (see Fig. 10.13).37

A final point to note relates to the magnitude of the peak premixed-burn heat-release rate and its relative timing (see Fig.
10.42 for an illustrative example). As in-cylinder gas conditions such as ρg and T g change, and as a consequence the ignition
delay shortens or lengthens, so the premixed-burn peak heat-release rate decreases or increases. With shorter delays, the
amount of rich fuel-vapor/entrained-air mixture within the sprays ready for spontaneous autoignition to occur decreases so its
chemical energy available for rapid release decreases. The mixing-controlled burning heat-release-rate profile then absorbs
the additional fuel to be burned in this second mode without major change. However, as the ignition delay lengthens
significantly (and the premixed-burn fuel amount increases substantially) then the mixing-controlled burning phase is more
noticeably affected.37

Ignition delay data from actual and simulated engine experiments have usually been correlated by equations of the form:

τid = Ap− n exp ( )

EA
R̃T

(10.33)

In general, τ id is a function of mixture temperature, pressure, equivalence ratio, and fuel properties (though no accepted form
for the variation with equivalence ratio is yet established). In the studies summarized and referenced in the first edition of this
text,1 the fuel was injected into a uniform air environment where the pressure and temperature only changed due to the
cooling effect of the fuel-vaporization and fuel-heating processes. In an engine, pressure and temperature change during the
delay period due to the compression resulting from piston motion. To account for the effect of changing conditions on the
delay the following empirical integral relation has been used:

tsi+ τid 1
∫ ( ) dt = 1
tsi τ

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(10.34)

where tsi is the time of start of injection, τ id is the ignition delay period, and τ is the ignition delay at the conditions pertaining
at time t. Whether the variation in conditions is significant depends on the amount of injection advance before TC that is used
and the length of the delay.

The first edition of this text1 compared several published Arrhenius equations for ignition delay of the form of Eq. (10.33). See
also Ref. 39. These earlier correlations no longer seem useful for several reasons. In-cylinder pressures and temperatures at
TC continue to change as turbocharging dominates and boost levels increase. Such conditions are difficult to realize in out-of-
engine experiments. Increasing injection pressures and high swirl in smaller high-speed DI engines are reducing the
contribution to the delay that these enabling physical processes contribute. Also, using a single Arrhenius expression to
represent the overall chemistry of the autoignition process is too simplistic given the complex chemistry actually involved.

An illustration of that chemistry is shown in Fig. 10.43 where a simpler hydrocarbon molecule n-heptane (C7H16), which has a
cetane number of 60 (close to that of diesel fuel which is about 50), was used diesel fuel surrogate. The detailed chemical
kinetic model (using 550 species and 2454 reactions) is briefly described in the reference.11 The chemistry calculation is at a
starting temperature of 900 K, pressure of 83 bar, and fuel-air equivalence ratio of 4, appropriate conditions for an
autoignition, and premixed-burn simulation in a fuel spray in a turbocharged diesel engine. Autoignition commences at about
0.03 msec (about 3° ASI) and the low-temperature first stage (and modest) energy release occurs (temperature rise of some
150 K). Just after 0.07 msec (7° ASI), the second stage of the ignition process (high-temperature) chemistry begins which
rapidly raises the temperature in the leading half of the spray plume to rise to 1650 K (see also Fig. 10.14), through a larger
energy release (raising the temperature by some 400 K or more). After 0.1 to 0.15 msec (1 to 1.5°) ASI, the rich mixture within
the spray contains H2O, CO2, CO, CH4, soot precursors (acetylene and polyacetylenes), and lower carbon atom hydrocarbons
(C3 and C4) along with some 60% nitrogen. By energy fraction (mass fraction × heating value), the combustibles H2, CO, CH4,
soot precursors, and lower carbon number hydrocarbons are 11, 21, 16, 40, and 12%, respectively, of the unreleased rich-
mixture chemical energy. Some 25% of the fuel's full heating value has been released at this point. This is the "fuel" on the fuel
side of the diffusion flame, during the mixing-controlled combustion phase.11

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 Figure 10.43 Results of chemical kinetic analysis of n-heptane vapor reaction with air, at ϕ = 4 and
initial mixture temperature of 900 K and pressure 83 bar (typical TC diesel engine conditions). The
evolving species concentrations and gas temperature in this rich mixture within each diesel spray
are shown over time (0 to 0.14 ms). 11

Such chemical-kinetic autoignition modeling studies indicate a strong dependence of reaction time scales on ambient
temperatures. For example, an increase from 750 K to 1000 K reduces reaction times from about 1 to 0.1 ms. Ignition delays
of some few degrees crank angle, 0.2 to 0.3 ms, are needed for normal diesel engine operation.11

10.5.4. Physical Factors Affecting Ignition Delay

The physical variables that control the development of the fuel spray, and the air-charge state (its pressure, temperature, and
velocity), will influence the ignition delay. These quantities depend on the design of the fuel-injection system and combustion
chamber, and the engine operating conditions. The injection system variables affecting the fuel-spray development are
injection timing, quantity, velocity, rate, drop size, and spray form or type. The relevant charge conditions depend on the
combustion system employed, the details of the combustion chamber design, inlet air pressure and temperature, compression
ratio, injection timing, residual gas amount and state, coolant and oil temperature, and engine speed. Data on these
interactions are available for different types of diesel engines. The trends observed with the different diesel combustion
systems are generally similar, though details may differ. In this section the ignition delay trends during fully warmed-up engine
operation are discussed. In modern diesel engines, ignition delays are short: a few crank-angle degrees. Thus, changes in
delay in warmed-up engines are now less significant. However, the dependence of the ignition delay on engine design and
operating variables during engine starting and warm-up is important, and may be different from fully warmed-up behavior due
to lower air temperatures and pressures.

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10.5.4.1. Injection Timing
At normal engine conditions (low to medium speed, fully warmed engine), the minimum delay occurs with the start of injection
at about 10° BTC. The increase in the delay with earlier or later injection timing occurs because the air temperature and
pressure change. If injection starts earlier, the initial air temperature and pressure are lower so the delay will increase. If
injection starts later (closer to TC) the temperature and pressure are initially slightly higher but then decrease as the delay
proceeds. The most favorable conditions for ignition lie in between.

10.5.4.2. Injection Quantity or Load

Figure 10.44 shows the effect of increasing injection quantity or engine load on ignition delay. The delay decreases
approximately linearly with increasing load for this DI engine. As load is increased, the residual gas temperature and the wall
temperature increase, as does heat transfer to the air charge during the first half of compression. This results in higher charge
temperature (and, to a lesser extent, charge pressure) at injection, thus shortening the ignition delay. When adjustment is
made for this increasing temperature, it is found that increasing the quantity of fuel injected has little significant effect on the
delay period under normal operating conditions. Under engine starting conditions, however, the delay increases significantly
due to the larger drop in mixture temperature: engine components are cold, there is no in-cylinder air heating, and significantly
more air cooling during compression. This latter result should be expected since evaporation of the injected fuel further
reduces mixture temperature.

Figure 10.44 Effect of inlet air pressure and temperature on ignition delay versus load in a small DI
diesel at 1980 rev/min. (a) Engine naturally-aspirated, and turbocharged with 1 atm boost (2 bar
absolute); inlet air temperature T i = 25°C; 50 cetane number fuel. (b) Engine naturally-aspirated; T i =
25 and 66°C; 34 and 50 cetane number fuel.40

10.5.4.3. Drop Size, Injection Velocity, and Rate

These quantities are determined by injection pressure, injector nozzle hole size, nozzle type, and geometry, but they have little
impact on the ignition delay. At normal operating conditions, increasing injection pressure produces only modest decreases in
the delay. Doubling the nozzle hole diameter at constant injection pressure to increase the fuel flow rate (by a factor of about
4) and increase the drop size (by about 30%) had no significant effect on the delay. Studies of different nozzle hole
geometries showed that the length/diameter ratio of the nozzle was not significant; nor did changes in nozzle type (multi-
hole, pintle, pintaux) cause any substantial variation in delay at normal engine conditions.38

10.5.4.4. Intake Air Temperature and Pressure

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10.5.4.4. Intake Air Temperature and Pressure
Figure 10.44 also shows values of ignition delay for diesel fuels for different charge temperatures and pressures at the time
of injection. The intake air temperature and pressure will affect the delay via their effect on charge conditions during the delay
period. The figure shows the effects of inlet air pressure and temperature as a function of engine load. The fundamental
ignition data available show a strong dependence of ignition delay on charge temperatures below about 1000 K at the time of
injection. Above about 1000 K, the data suggest that the charge temperature is no longer as significant. Through this
temperature range there is an effect of pressure at the time of injection on ignition delay: the higher the pressure the shorter
the delay, with the effect decreasing as charge temperatures increase and delay decreases. Since air temperature and
pressure during the delay period are such important variables, other engine variables that affect the relation between the
intake air state and the charge state at the time of injection will influence the delay. Thus, an increase in the compression
ratio will decrease the ignition delay, and injection timing will affect the delay (as discussed above), largely due to the
changes in charge temperature and pressure at the time of injection.

10.5.4.5. Engine Speed

Increases in engine speed at constant load result in a slight decrease in ignition delay when measured in milliseconds; in
terms of crank-angle degrees, the delay increases almost linearly. A change in engine speed changes the temperature/time
and pressure/time relationships. Also, as speed increases, injection pressure increases. The peak compression air
temperature increases with increasing speed due to smaller heat loss during the compression stroke.40

10.5.4.6. Combustion Chamber Wall Effects

The impingement of the spray on the combustion chamber wall obviously affects the fuel evaporation and mixing processes.
Impingement of the fuel jet on the wall occurs, to some extent, in almost all of the smaller, higher speed engines (see Fig.
10.40). Engine and combustion bomb experiments have been carried out to explore the effect of wall impingement on the
ignition delay. There does not seem to be a consistent trend. When the evolving fuel spray impinges on the combustion bowl
wall, there will be some cooling of the spray tip. However, with short delays (in warmed-up engines) autoignition usually
occurs before any significant spray-wall interaction.

10.5.4.7. Swirl Rate

Changes in swirl rate change the fuel evaporation and fuel-air mixing processes (see Figs. 10.23 and 10.24). They also
increase wall heat transfer during compression and, hence, reduce the charge temperature at injection. While engine studies
of the effect of swirl rate on ignition delay have been made, only limited data are available. At normal operating engine
conditions, the effects of swirl rate changes on the delay are small. Under engine starting conditions (low engine speeds and
compression temperatures), the effect is more important, presumably due to the higher rates of evaporation and mixing
obtained with swirl.

10.5.4.8. Oxygen Concentration

The oxygen concentration in the charge into which the fuel is injected would be expected to influence the delay. The oxygen
concentration is changed, for example, when exhaust gas is recycled to the intake for the control of oxides of nitrogen
emissions (see Sec. 11.2.4). Results of a study carried out in a single-cylinder DI engine operated at a constant air/fuel ratio
(30:1), manifold temperature, injection timing, and speed (1800 rev/min), where the oxygen concentration was varied by

41

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recirculating known amounts of cooled exhaust, are shown in Fig. 10.45. 41 Oxygen density is normalized by the naturally-
aspirated no-recirculation test value. As oxygen concentration is decreased, ignition delay increases.

Figure 10.45 Effect of oxygen density in gas on ignition delay in single-cylinder DI engine of 1.3-dm3
displacement with rc = 15 at 1800 rev/min. Oxygen density changed by recycling exhaust gas at
constant inlet density and by varying inlet pressure from 0.5 to 3 atm with air.41

10.5.5. Effect of Fuel Properties

10.5.5.1. Diesel Fuel
Since both physical and chemical processes take place during the ignition delay, the effects of changes in the physical and
chemical properties of fuels on the delay period have been studied. The chemical characteristics of the fuel are much the
more important. The ignition quality of the fuel, defined by its cetane number, will obviously affect the delay. The dependence
of cetane number on fuel molecular structure is as follows. Straight-chain paraffinic compounds (normal alkanes) have the
highest ignition quality (autoignite more quickly), a trend which improves as the chain length increases. Aromatic compounds
have poor ignition quality as do the alcohols (hence, the difficulties associated with using methanol and ethanol, possible
alternative fuels, in compression-ignition engines). Figure 10.46 illustrates these effects. A base fuel was blended with pure
paraffinic (normal, iso-, and cycloalkanes), aromatic, and olefinic hydrocarbons of various carbon numbers, by up to 20% by
volume. The base fuel, a blend of 25% n-hexadecane and 75% isooctane, had a cetane number of 38.3. The figure shows that
the resulting ignition delays correlate well as a function of cetane number at constant compression ratio and engine operating
conditions. Addition of normal alkanes (excluding n-pentane and lower carbon number alkanes) improves the ignition quality.
As the chain length of the added paraffin gets longer (higher carbon number) the cetane number improvement increases.
Isoalkanes, depending on the degree of branching, degrade ignition quality (unless the branching is concentrated at one end
of the molecule, when these types of isoalkanes improve ignition quality). Cycloalkanes and aromatics generally reduce the
cetane number, unless they have a long n-alkane chain attached to the ring. The cetane number of a fuel (a measure of its
ability to autoignite) generally varies inversely with its octane number (a measure of its ability to resist autoignition; see Fig.

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9.65 for the effect of hydrocarbon structure on knock). The cetane number of commercial diesel fuel is normally in the range
of 40 to 55.

Figure 10.46 Effect of type of hydrocarbon structure on ignition quality of fuels in DI diesel
combustion process at constant compression ratio and engine operating conditions.42

Cetane number is controlled by the source of crude oil, by the refining process, and by additives or ignition accelerators. Just
as it is possible to reduce the tendency to knock or autoignite in spark-ignition engine fuels by adding antiknock agents, so
there are additives that improve the ignition quality of compression-ignition engine fuels. Generally, substances that increase
the tendency to knock enhance ignition, and vice versa. Ignition-accelerating additives include organic peroxides, nitrates, and
nitrites. The most important of these commercially are the alkyl nitrates (isopropyl nitrate, primary amyl nitrates, primary hexyl
nitrates, octyl nitrate). Typically, about 0.5% of these additives by volume in a distillate fuel gives about a 10 cetane number
increase in a fuel's ignition quality, though their effectiveness may depend on the composition of the base fuel. The
incremental effect of increasing amounts of ignition-accelerating additives on cetane number decreases.40 Usually, the
ignition delay obtained with cetane improved blends are found to be equivalent to those obtained with natural diesel fuels of
the same cetane number. Two potential practical uses for ignition accelerators are in upgrading the ignition characteristics of
poorer quality diesel fuel and (in much larger amounts) making possible the use of alcohols in compression-ignition engines.

The physical characteristics of diesel fuel do not significantly affect the ignition delay in fully or partially warmed-up engines.
Tests with fuels of different front-end volatility (over the cetane number range 38 to 53), and with substantially different front-
end ignition quality for the same average cetane number, showed no discernible differences. Fuel viscosity variations over a
factor of 2.5 also showed no significant effect.40 Thus, in a warmed-up engine, variations in fuel atomization, spray
penetration, and vaporization rate over reasonable ranges do not appear to influence the duration of the delay period
significantly (see also Sec. 10.4.6 on fuel spray evaporation).

10.5.5.2. Biodiesel
An alternative to petroleum-derived diesel fuel is biodiesel. The term refers to a vegetable oil or animal-fat based fuel
consisting of long-chain alkyl (methyl or ethyl) esters.[3] These are made by chemically reacting lipids (e.g., vegetable oils,
animal fats) with methanol or ethanol. While similar in behavior to diesel fuel, these are differences. The vegetable oils used in

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biodiesel production differ in the composition of their fatty acids, and differences in the pretreatment of these oils and the
biodiesel production process also cause variations in properties.

Biomass sources used to produce vegetable oils for biodiesel production include rapeseed, soybeans, sunflower seed, palm
and coconut oils. Highest yields come from palm oil (4500–5000 liters/hectare) with coconut about half that, and the others
listed above in the 500 to 1000 l/ha range. Present expectations are that an upper bound on biodiesel productions is about
10% of petroleum diesel.

Biodiesel is currently mostly blended with conventional diesel to minimize the impact of its somewhat different
characteristics. Five to ten percent blends (B5 and B10) are commonly used. B100 can be used in diesels but engine
modifications would be required.

The characteristics of biodiesel that could affect combustion in diesel engines are its physical and chemical properties. Its
molecular size (C16–C18) is in the diesel fuel range (C10–C20), but its boiling point is higher. Its viscosity is higher than that of
diesel fuel. It has about 10% lower energy content per unit mass or volume (lower heating value varies with composition but is
about 38 MJ/kg). Its cetane number (46 to 60) is higher than that of standard diesel fuel (40 to 55). It has better lubricating
properties than diesel due to its higher viscosity. It is, however, a more aggressive solvent, and is less resistant to oxidation so
its "shelf life" is significantly more limited. Its use blended in modest amounts with petroleum-based diesel fuel is thus a
pragmatic approach. 43, 44

10.5.6. Correlations for Ignition Delay in Engines

Many correlations have been proposed for predicting ignition delay as a function of engine and air charge variables. These
usually have the form of Eq. (10.33) and have been based on data from more fundamental experiments in combustion vessels
and flow reactors. An important factor in assessing the appropriateness of any correlation is how it is to be used to predict the
magnitude of the delay. If an equation for predicting the complete delay process (including all the physical and chemical
processes from injection to combustion) is required, then the data show that such a simple form for the equation is unlikely to
be adequate for the full range of engine condition. Much more detailed chemical-kinetic models for the autoignition process
of a premixed fuel-air mixture during the delay period are being used in conjunction with models for the physical processes of
fuel evaporation and fuel-air mixing to predict the evolving spray processes.

An empirical formula, developed by Hardenberg and Hase45 for predicting the duration of the ignition delay period in DI
engines, has been shown to give reasonable agreement with experimental data over a wide range of engine conditions (see
Fig. 10.47).46 This formula gives the ignition delay (in crank-angle degrees) in terms of charge temperature T (kelvins) and
pressure p (bar) during the delay (taken as TC conditions) as

¯¯¯p ) exp [EA ( 1 − ]

0.63
1 21.2
τid(CA ) = (0.36 + 0.22S )+( )
R̃T 17, 190 p − 12.4

(10.35)

where
¯¯¯p is the mean piston speed (meters per second) and
S
R̃ is the universal gas constant (8.3143 J/mol · K). EA (joules per mole) is the apparent activation energy, and is given by

618, 840
EA =
CN + 25

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(10.36)

where CN is the fuel cetane number. The apparent activation energy decreases with increasing cetane number. The delay in
milliseconds is given by

τid(CA )
τid(ms) =
0.006N

where N, engine speed, is in revolutions per minute. Values for T and p can be estimated using a polytropic model for the
compression process:

TTC = Tirnc − 1, pTC = pirnc

(10.37a,b)

where n is the polytropic exponent, rc is the compression ratio, and the subscript i denotes intake manifold conditions. Values
of the polytropic exponent are given in Fig. 10.48 for a direct-injection diesel under warm and cold engine operating
conditions.41, 46

Figure 10.47 Comparison of engine ignition delays predicted with Eq. (10.35) with corresponding
measured values. 46

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 Figure 10.48 Exponent n for polytropic model of compression process in Eq. (10.37) and
corresponding end-of-compression air temperature at TC. Warm and cold DI diesel engine with 130-
mm stroke.45

[1] In the original procedure α-methyl-napthalene (C11H 10) with a cetane number of zero represented the bottom of the scale.
Heptamethyl-nonane, a more stable compound, has replaced it.
[2] API (American Petroleum Institute) gravity is based on specific gravity and is calculated from: API gravity (degrees) = 141.5/(specific
gravity at 60°F) − 131.5.
[3] These are usually fatty acid methyl ester (FAME) and fatty acid ethyl ester (FAEE).

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