Experimental Thermal and Fluid Science 34 (2010) 338345

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Experimental Thermal and Fluid Science

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Comparison of electrical and laser spark emission spectroscopy for fuel

concentration measurements
C. Letty a,*, A. Pastore a, E. Mastorakos a, R. Balachandran b, S. Couris c
a
Engineering Department, University of Cambridge, Trumpington Street, Cambridge CB2 1PZ, UK
b
Mechanical Engineering, University College London, UK
c
Physics Department, University of Patras, and ICEHT/FORTH, Greece

a r t i c l e i n f o a b s t r a c t

Article history: Emission spectra from electrical and laser sparks in owing methaneair mixtures of various composi-
Received 13 October 2009 tions have been collected and analysed. The differences and similarities between the electrical and laser
Accepted 16 October 2009 sparks in the context of their emission are discussed. The emission spectra from the laser spark were
characterized by a weak continuum, onto which several strong atomic lines and some molecular bands
were superimposed, in contrast to the spectra of electrical spark where a strong continuum, few atomic
Keywords: lines and several strong molecular bands were evident, making thus the laser spark spectroscopy a more
Electrical spark
accurate technique to measure hydrocarbon concentration. For both types of spark, the total intensity of
Laser spark
Spectroscopy
the CN chemiluminescence around 388 nm was found to correlate almost linearly with fuel concentra-
Fuel concentration tion in methaneair mixtures.
2009 Elsevier Inc. All rights reserved.

1. Introduction maturity of the technique, detailed information on the nature of

The creation of a spark in a gas may result in ame ignition, if
the spark is strong enough and the gas mixture falls within the
ammability limits. The energy deposited by the spark results in
plasma formation that generates radicals and ionised species
which can then trigger chemical reactions and further heat release,
in the case of ammable mixture. Even in the case of mixtures that
would not normally allow self-sustaining combustion, a spark will
result in a short-lived concentration of various intermediates, such
as fuel fragments (e.g. CN*) and hydroxyl radicals (OH*) [1].
The spark is always associated with some form of light emis-
sion. If the spark is created by an electrical arc, then the initial
breakdown phase results in strong emission. This phase lasts usu-
ally of the order of a few micro-seconds [2]. The subsequent glow
discharge phase, during which most of the energy is usually depos-
ited and which typically lasts 100500 ls, also results in light
emission, although this is now less strong. The electrical spark is
the most common way to initiate combustion and has been very
widely studied, mostly in terms of the minimum ignition energy
necessary to ignite a given mixture as a function of the spark
parameters such as electrode material, shape, distance, spark dura-
tion and electrical circuitry (e.g. capacitor or self inductance), and
as a function of ow parameters such as equivalence ratio, velocity,
turbulence level, pressure, and temperature [35]. Despite the
* Corresponding author. Tel.: +44 1223 765 212.
E-mail addresses: cl447@cam.ac.uk (C. Letty), em257@eng.cam.ac.uk (E. Mastor-
akos).
the emission is not widely available.
Another way to generate a spark is by focusing the beam of a
(usually) Q-switched nanosecond laser. This so-called laser igni-
tion has been studied extensively [68]. Several advantages of laser
ignition compared to the electrical spark can be pointed out: the
location of the spark can be chosen arbitrarily inside the combus-
tor, there are no quenching effects by the spark plug electrodes
which result in an easier ignition of lean mixtures, and the time
of the spark and the deposited energy are easy to control. Due to
the very short laser pulse duration, which is usually of the order
of a few nanoseconds, laser ignition has shorter ignition delay
and reduced total combustion duration compared to conventional
spark ignition [911]. Laser ignition enables a multiple point igni-
tion, which may result in more efcient combustion [8], and the
early ame velocity in laser ignited gas mixture is faster than that
in conventionally ignited mixtures [10].
Spectroscopic studies of both electrical and laser sparks have
been performed to understand better the nature of the processes
involved, but also to examine the possibility to use the emitted
light characteristics as a tool to measure the fuel concentration.
This technique may be called Spark Induced Breakdown Spectros-
copy (SIBS) or, more specically, Laser Induced Breakdown Spectros-
copy (LIBS) in the case of a laser spark. The radiation that escapes
from the spark can arise from atomic and/or molecular species.
Among the various emitting species, unstable radicals such as
CH*, C2*, and CN* contribute appreciably in the spectral regions
of visible and near UV regions. SIBS has been used by Fansler
et al. [12] for the analysis of the emission during the initial

0894-1777/$ - see front matter 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.expthermusci.2009.10.018
 C. Letty et al. / Experimental Thermal and Fluid Science 34 (2010) 338345
breakdown or the subsequent discharge phase. They have used a
gated detector to measure the emitted light at various instants
from the initiation of the spark in a gasoline engine (from top-dead
centre to 14 before TDC at 2000 rpm). Several excited molecular
species (NO*, OH*, NH*, CN* and CH*) were observed in their spec-
tra. The authors found that CN* is the most sensitive molecule to
fuelair ratio and that the spark-energy-normalized CN* emission
intensity evolves nearly linearly with the equivalence ratio. A cal-
ibration procedure was thus elaborated that did not require re-cal-
ibration if changes occur (gas density, pressure, temperature or
spark advance). It relied on the assumption that CN intensity is
most directly related to the carbon number density at the spark.
The technique provided an approximate measurement of the
equivalence ratio / at the location of the spark, which can then
be used to diagnose the subsequent engine behaviour. The preci-
sion of a single measurement, however, was not very good, possi-
bly due to the very difcult environment of an engine. It would be
interesting to examine further this technique with simpler fuels
and open ames in order to explore further its capabilities and this
is one of the aims of the present paper.
Laser Induced Breakdown Spectroscopy (also known as Laser In-
duced Plasma Spectroscopy) is a non-intrusive diagnostic. The
principle of LIBS is based on the creation of a microplasma where
atoms/ions are excited. The detection of the emitted radiation al-
lows for the determination of media composition under some con-
ditions. The LIBS technique has a high sensitivity for many
elements [13]. The high temporal and spatial resolution of the LIBS
technique makes it particularly well-suited for the study of com-
plex phenomena such as ames. Qualitative or quantitative mea-
surements can be carried out by recording and analysing the
obtained spectra. For example, LIBS measurements allow the calcu-
lation of electronic temperature, electrons density, and species
concentration [14]. The LIBS signal may present uctuations [14]
due to the shot to shot laser energy instability and/or the inhomo-
geneity of the sample, particularly in the case of solid samples,
which is the most difcult to compensate. When LIBS occurs in
gases with uniform composition some stochasticity in the micropl-
asma size and characteristics may be expected. LIBS measurements
in turbulent ows with inhomogeneities at the scale of the
microplasma have not been performed systematically. Recent
developments of LIBS aim to determine the equivalence ratio in
combustion environments. Ferioli et al. [15] measured atomic line
intensities (C, N and O) and derived time-resolved equivalence ra-
tio measurements in the exhaust stream of a spark-ignition engine.
Sturm and Noll [16] applied LIBS for the determination of ratios of
the elements C, H, N and O in several atmospheric pressure gas
mixtures. Phuoc and White [17] used measurements of the inten-
sity ratio of the Ha line at 656.3 nm and the O(I) triplet line near
777 nm in order to determine the axial and radial distribution of
equivalence ratio in a turbulent methane jet diffusion ame. These
applications were dedicated to the determination of the fuelair
ratio and used a calibration curve. A change in the optical setup
(i.e. the laser energy, the laser focusing conditions, etc.) will create
different plasma for a similar spark energy. Therefore the calibra-
tion curve may not be transposed to different experiments. Online
data may be used to compute the plasma characteristics. Stavropo-
ulos et al. [18] having determined the plasma temperature and
electronic density and veried that Local Thermodynamic Equilib-
rium (LTE) could be reasonably assumed, have shown that the
equivalence ratio of methaneair mixtures can be quantitatively
determined from the ratio of the number densities NH/NO, the lat-
ter being obtained from the ratio of the hydrogen (Ha at 656 nm)
and oxygen (O(I) at 777 nm) atomic lines intensities.
Both SIBS and LIBS applications performed so far used spec-
trometers using intensied charged coupled devices (ICCD) allow-
ing for the temporal gating of the signal. Ungated emission
339
measurements [19] have also been used for LIBS and it was found
that reasonable measurements of the H/O ratio in ames could be
made. This opens the way that a cheaper technique, more amena-
ble to aggressive industrial environments could be developed. The
objectives of the present work are (i) to investigate the character-
istics of ungated spectra emitted from electrical and laser sparks in
homogeneous air-methane mixtures, which allows a detailed com-
parison between the two types of sparks in the context of their
emission; and (ii) to examine various ways of analysing these spec-
tra to infer the local fuel concentration. The structure of this paper
is as follows. First, experimental methods are presented, followed
by the procedures for data post-processing. Finally, the results
are presented and discussed.
2. Experimental methods
2.1. Flow considered
A homogeneous owing methane/air mixture is used. The ow
comes out of a 25 mm ID tube (29 mm OD) placed inside a tube of
50 mm ID in which nitrogen ows at 0.25 m/s. All ows were mea-
sured by calibrated rotameters with a maximum uncertainty of 5%.
The methane comes from a bottle with 99% purity. The volumetric
composition of the fuelair mixture can be adjusted and character-
ized by the volume fraction of methane, XF, which took values from
0 to 1. For each condition, the velocity of the ow is kept constant
at 1.9 m/s. The spark (see below) is created at the axis of the tube,
approximately 5 mm from the exit, which is too close for any
entrainment from the co-ow and hence we consider the mixture
at the spark as fully homogeneous.
2.2. Spark generation
The electrical spark was generated between two tungsten elec-
trodes (1 mm in diameter and 1 mm gap). The spark unit produced
repeatable sparks whose energy and duration could be varied inde-
pendently, with more information on the unit and its usage for tur-
bulent non-premixed ames given in Refs. [4,5]. The spark used in
the present work had 400 ls duration and 100 mJ estimated en-
ergy. Previous work showed that the energy of the sparks produced
by the ignition unit were within about 0.8%, which demonstrates
the high repeatability of the ignition system [4]. In the framework
of this paper, repeated sparks were used at a frequency set to 1 Hz
or 10 Hz. The laser spark was created by focusing the beam from an
8 ns Q-switched Nd-YAG laser (Continuum Surelite) operating at
1064 nm, at 10 Hz with a 150 mm focal length biconvex quartz
lens of 50 mm diameter. The laser energy per pulse was 370 mJ,
ensuring the generation of a laser spark at each laser shot under
all the experimental conditions used in this work, which are sum-
marized in Table 1.
2.3. Emission collection
The emitted light collected by a 76 mm focal length lens having
50 mm diameter was focused on the entrance slit of a spectrometer
(Ocean Optics USB 2000) equipped with a linear CCD array detector
operating in the 178877 nm spectral region with a spectral reso-
Table 1
Experimental conditions.
Electrical spark Laser spark
Spark frequency fe[0.5; 10] Hz f = 10 Hz
Energy 100 mJ 370 mJ
Integration time 1s 3 ms
Number of samples 10 20
340 C. Letty et al. / Experimental Thermal and Fluid Science 34 (2010) 338345
lution of 0.34 nm. As far as electrical spark ignition is concerned,
the spectra were collected for a period of 1 s. Each spectrum repre-
sents the average of ten samples for each case. A fast photodiode
was used to trigger each acquisition cycle with the ring of the la-
ser pulse. The light was collected over an interval of 3 ms starting
from the laser pulse. Each spectrum shown represents the average
of twenty samples for each case.
2.4. Data analysis
For the accurate wavelength calibration of the spectrometer the
atomic spectral lines from a Hg lamp have been used together with
some of the identied lines present in the measured spectra, as for
example the Ha at 656 nm, the Yb at 486 nm, the O(I) lines at
777 nm and the N(I) lines at 744 nm [20,2223]. In order to ensure
that no second order interferences are occurring in the measured
spectra, several appropriate high pass lters have been used. The ac-
quired spectra are not corrected for the spectral response of the opti-
cal setup. The shot to shot laser energy variation was measured and
found to be less than 5%, which is typical for Nd:YAG lasers.
The second stage of processing involved the correction for the
plasma intensity from shot to shot (Correction 1). In Ref. [21], the
evolution of the ratio of the intensity of the two rst elements of
the Balmer series (at 486 and 656 nm) versus the equivalence ratio
was studied. The authors noticed that the ratio H/N varied between
2.5 and 3.5 depending on Ha/Hb for a given equivalence ratio
(/ = 0.4). For higher values of Ha/Hb ratio changes tend to be smal-
ler. Their study showed that hydrogen excitation within the created
plasma should be the parameter to measure to retrieve correctly
the fuelair ratio. In the framework of this paper, the peak to peak
intensity of the rst two elements of the Balmer series is used in or-
der to take into account the variation in shot to shot laser energy.
In order to correctly evaluate the intensity of the spectral lines
of interest the contribution of the broad continuum has been sub-
tracted by dening for each spectral line a region of interest (de-
ned around its center) and subtracting the corresponding
continuum underneath (Correction 2, see Fig. 1). Then, the remain-
ing area under the peak was calculated and associated with the
number density of the corresponding species. This was necessary
in the case of the electric spark as the corresponding spectra exhib-
ited a prominent continuum often of comparable intensity to that
of the spectral line of interest. In fact, the delay of measuring and
the temporal gating of the signal several hundreds of nanoseconds
or few ls after the laser ring which is used when ICCD detectors
are employed is performed exactly in order to reduce the contribu-
tion of the continuum which affect the correct evaluation of the
strength of the spectral lines. Therefore, the key quantities that will
Fig. 1. Data pre-processing of typical spectral peaks. Solid line: raw spectrum;
dashed-line: removed contribution.
be used here for the determination of the fuelair ratio (or the fuel
concentration) are the area under the peaks of various molecular
bands or atomic lines and in particular those of CN* chemilumines-
cence (i.e. 370395 nm), and the ratio of the intensities of various
lines such as: RH/H = I (656 nm)/I (486 nm), RH/O = I (656 nm)/I
(777 nm) and RC/O = I (247 nm)/I (777 nm).
3. Results and discussion
3.1. Electrical spark
The inuence of the frequency of the electrical spark and the
methane mole fraction (XF) on the emitted light was investigated.
In Fig. 2 some spectra are shown corresponding to methane mole
fraction XF = 25% for various operational frequencies of the electri-
cal spark. It is evident that increasing the repetition rate of spark-
ing in the range 010 Hz a continuum emission is build up that, at
the maximum frequency examined here, becomes dominant.
Then, the electrical spark has been operated at 1 Hz and 10 Hz,
and for each frequency the methane mole fraction XF was varied up
to 25%. Fig. 3a, b present some representative spectra obtained for
different XF values. As can be seen from these spectra, when the
spark operates in air, the observed emission is dominated by a rel-
atively low intensity broad continuum between 300 and 800 nm,
which increases with the repetition rate and the methane mole
fraction. Superimposed on this continuum, several lines are clearly
visible. Based on their spectral shapes and characteristics and tak-
ing into account their regularity, it is reasonable to attribute them
to molecular emissions, although more detailed assignments have
not been tried at this preliminary stage of the work. In addition to
these spectral features, when fuel is present, several atomic lines
are also appearing and have been identied, as for example the
strong atomic hydrogen lines Ha and Hb at 656 and 486 nm respec-
tively, the carbon atomic line (C(I)) at 247 nm, and the oxygen (O(I))
triplet line at 777 nm, the last one being usually obscured by the
broadband emission. We noticed, however, that its intensity com-
pared to the continuum emission becomes the highest when the
fuel proportion is below the ammability limit. Then, it decreases
as the amount of fuel increases. Surprisingly, the continuum emis-
sion was observed to be particularly strong for the mixture XF = 5%
(at f = 1 Hz) and for XF = 15% (for f = 10 Hz), values close to lower
and upper ammability limits of methane in air.
The strong emission band at 380390 nm, peaked at 388 nm, is
attributed to the CN* chemiluminescence associated with the for-
mation of the CN* molecule. As expected, this emission is absent
from the spectrum corresponding to pure air, since the CN* mole-
cule is produced only during ignition and combustion. As a result,
CN* is present when fuel is present. In the spectra of Fig. 3, the
growth of the CN* band with the amount of fuel in the mixture
is evident. Moreover, in rich mixture (i.e. richer than the rich am-
mability limit, which corresponds to about 9.5% by vol.), the
growth of the Ha line as the fuel proportion increases can be seen
as well. The presence of H atoms in rich mixtures is due both to
combustion products (namely H2O) and fuel excess.
From the above, it is evident that: (i) electrical spark spectra ex-
hibit (at least) some of the expected atomic lines, (ii) in the spectra
corresponding to fuel-containing mixtures there is an important
contribution from CN* emission (consistent with [12]), which in-
creases with the amount of fuel present, and (iii) a strong contin-
uum exists in all cases.
3.2. Laser spark
Laser-induced spark spectra have been recorded for a volume
fraction of fuel varying from 0% to 16% with a step of 0.4% (see
 C. Letty et al. / Experimental Thermal and Fluid Science 34 (2010) 338345 341

Fig. 2. Spectra from electrical spark (at XF = 25%) for different spark frequencies.

Fig. 4). It is clear that LIBS spectra are very sensitive to the compo-
sition of the mixture since a very clear evolution exists as the fuel
concentration increases. In fact, increasing the fuel content in the
mixture, all the spectral lines become stronger (except N at
744 nm and O(I) at 777 nm) while some of them are getting also
larger probably because of the increasing role of the interactions
taking place as the concentration of fuel molecules increases.
In contrast to what was observed in the electrical spark spectra,
no appreciable broadband continuum emission was observed in
the LIBS spectra, although the repetition rate of the laser was the
same as for the electrical spark for all fuel contents. In addition,
the spectra are very clear. Fig. 5 shows some of the peaks in greater
detail. The rst observation is that the LIBS spectra are character-
ized by sharper lines than those observed in the SIBS spectra. For
the LIBS spectra in air, even without any fuel, a line at 247 nm
(see Fig. 5a) assigned to C(I) line is observed. Its presence without
any fuel is due to the carbon atoms arising from the carbon dioxide
molecules (CO2) which are present in air and dissociate in the

Fig. 4. Spectra from laser spark (at f = 10 Hz) for different chosen mixture
Fig. 3. Spectra from the electrical spark for different mixture compositions and the compositions (volume fuel fractions ranging from 0% to 16% by step of 0.4%-richest
indicated spark frequency. mixture: 18%-were recorded).
342 C. Letty et al. / Experimental Thermal and Fluid Science 34 (2010) 338345
formed plasma within the focal volume of the laser beam. In addi-
tion, the Ha line at 656 nm (see Fig. 5c), the O(I) line at 777 nm and
some nitrogen (N(I) at 744 nm) lines are clearly visible (see Fig. 5d).
At longer wavelengths, some other weaker lines are visible,
namely, a carbon (C(I)) line at 833.5 nm, an oxygen (O(I)) line at
844.6 nm and some nitrogen (N(I)) lines between 855 and
875 nm. These last are often used for the determination of the plas-
ma temperature [24]. Moreover, two molecular bands are clearly
visible, one assigned to the CH* emission at about 431 nm and
the most prominent one at 388 nm corresponding to CN* radical
emission.
With increasing fuel concentration the general trend observed
was that the C line at 247 nm, the CN* band at 388 nm, the CH*
(I)
band at 431 nm and the hydrogen line Ha at 656 nm are increasing
as well. Simultaneously, exactly the opposite trend was observed
for the nitrogen and oxygen lines at 744 and 777 nm respectively.
These spectral lines were found continuously decreasing (see
Fig. 5d) as the ratio of fuel to air in the mixture was increasing.
As a result, it can be concluded that the LIBS spectra qualitatively
reproduce the expected trends concerning the correlation of the
intensity of the observed spectral lines to the fuel content present
in the spark location. It has to be noticed as well that LIBS spectra
suffer from much weaker continuum emission compared to the
SIBS spectra and that both atomic lines and molecular bands are
Fig. 5. Close view of peaks in laser spark spectra for the indicated fuel volume fraction.
readily observed. The present LIBS spectra are similar to those re-
ported in Ref. [1] (e.g. their Fig. 13, emission spectrum at 2 ls after
breakdown with a time integration of 1 ms).
3.3. Comparison of laser spark to electrical spark spectra
Concerning the comparison of the intensities of the LIBS spectra
with the corresponding SIBS spectra several parameters should be
taken into account. First, the spectra presented in this work have
been measured using different integration times for the detector.
In particular, all the LIBS spectra presented here were measured
using 3 ms integration time, while for the SIBS spectra the integra-
tion time was set to 1 s. The integration times were chosen in order
to obtain a reasonable signal to noise ratio. Therefore, although the
same optical setup has been employed no direct comparison of
respective intensities can be done.
Another important issue that has to be considered is that the
plasmas produced are in principle very different since they result
from different processes operating at different time scales. The en-
ergy deposited in the plasma and therefore the excitation/ionisa-
tion and fragmentation processes occurring will be different. It
results that the plasma-characteristic parameters such as the plas-
ma temperature, the electronic density, its temporal evolution, the
 C. Letty et al. / Experimental Thermal and Fluid Science 34 (2010) 338345 343

plasma volume, etc., will be very different, affecting strongly the

intensity and the spectral distribution of the emitted radiation.
Concerning the emission of the laser produced plasmas, it is
known that during the early stages just after the plasma creation,
i.e. the rst few hundred nanoseconds, the emission is very strong,
often not allowing the observation of the atomic lines. As time
evolves, the plasma cools down, but because the background emis-
sion decreases more rapidly than the atomic line emissions with
the decrease of the temperature, the atomic lines survive for longer
times and therefore they can be measured free from background
continuum interferences. In the case of the electrical spark, the sit-
uation can be very different as plasma is formed under completely
different conditions. The rate of deposition of the electrical power
into the plasma is very different than in the case of laser induced
breakdown therefore resulting in a plasma state characterized by
different parameters, as e.g. plasma temperature, electronic den-
sity, etc. These issues are not examined here but they must be
examined in the future.
In any case, concerning the strong continuum present in the
spectra of electric sparks a possible explanation could be thermal
origin emission radiated from the heated electrodes due to the
high currents which are developed during operation of the spark
and/or from deposit material on the electrodes (e.g. soot) [25].
Contribution from electrode evaporation, although it can not be ex-
cluded, seems less probable because of the very low sputtering rate
of tungsten limiting the possibility of tungsten atoms spectral lines
[26]. In fact, we have not succeeded to observe any tungsten lines
in the measured spectra.
In combustion processes, usually, appreciable amounts of OH*
radicals are produced either during the primary stage of combus-
tion or when it is involved as third partner in a recombination reac-
tion. However, in the present experiments no strong OH* emission
(at 308 nm) has been observed in both the electrical spark and la-
ser spark spectra. Only a low intensity band was evident at 308 nm
in the LIBS results (see e.g. Fig. 4) in agreement with [1].

3.4. Determination of fuel concentration

In Ref. [12] it was found that the total intensity of the CN* band
(calculated from the integral of the area under the peak after taking
into account the continuum contribution) normalized by the
amount of energy dissipated in the electrical spark, correlated lin-
early with the equivalence ratio (in the range 03) in a spark-igni-
tion direct-injection engine. In these experiments, the acquisition
timing was carefully chosen in order to prevent the camera gate
to overlap the sharp voltage peak occurring during the breakdown.
That is the emitted light was collected after the breakdown.
* tio determination.
 Fig. 6R shows the  variation of the CN band total intensity
395
ACN;a 370 Ikdk from the electrical spark spectra at 1 and
10 Hz, versus the amount of fuel. Because of the presence of a
broadband continuum in electrical spark spectra, post-processing
is applied to remove this contribution (see Section 2.4). Although
some scatter of the experimental points is obvious and saturation
probably occurred at large amounts of fuel, in particular at the
operation frequency of 10 Hz, both curves exhibit a reasonably lin-
ear dependence with fuel content.
 In Fig.R 7, the variation
 of the total intensity of the CN* band
395
ACN;a 370 Ikdk versus fuel mole fraction for the laser spark
measurements is presented. It is evident that a linear correlation
is obtained and the scatter of the experimental data is reduced sig-
nicantly, while no saturation effects are observed even at the
highest fuel contents examined. Fig. 7 also includes some atomic
R 440
line peak ratios and data for ACN;b 340 Ikdk and
R 500
ACN;c 300 Ikdk obtained from the LIBS spectra. Using a wider
range of wavelengths allows more spectral peaks and hence offers
a higher signal, although there is less direct relation with a specic
Fig. 6. Evolution of CN* area extracted from electrical spark spectra (i.e. between
370 and 395 nm) versus the amount of fuel in the mixture.
carbon-containing molecule and hence is more difcult to inter-
pret. It is interesting, however, that these wider ranges can also
provide a reasonable linearity of emission with fuel concentration
and hence these, too, could in principle be used for equivalence ra-
From the above it becomes evident that the CN* total emission
can be used as a tool for the determination and/or monitoring of
the methane content in a methaneair mixture. Similar results
have been found and reported in Refs. [18,19]. In the former, a lin-
ear correlation has been found between the ratio RH/O and the
equivalence ratio in premixed laminar methaneair ames. In
the latter study a linear dependence of the spectral peak ratio on
the equivalence ratio has been found. Note that the equivalence ra-
tio / is not proportional to XF; these two quantities are related by
X F 1X F;st
/ 1X F X F;st
, with XF,st = 9.524% for CH4/air combustion. Therefore
we cannot expect the techniques discussed here to provide a linear
signal both for the concentration of fuel and for the carbon to oxy-
gen ratio. However, the deviation of linearity from the above equa-
tion in the range of / studied is smaller than the experimental data
scatter in Fig. 7 and in most of the references quoted here, suggest-
ing that the good comparison between the ACN and the H/O ratio
shown in Fig. 7 is further evidence of the accuracy of the CN* area
technique examined here.
344 C. Letty et al. / Experimental Thermal and Fluid Science 34 (2010) 338345
Fig. 7. Evolution of CN* area (ACN,a, ACN,b, ACN,c) and H/O ratio extracted from laser spark spectra versus the mole fraction of fuel in the mixture.
The evolution, from experimental data, of the fuel content in the
mixture shows signicant scatter, which is about 10% (linear curve
ts have correlation coefcients about 0.9). The error in air and fuel
ow rate measurement lead to an error on the global equivalence
ratio inferior to 1%. For both electrical and laser spark, the integra-
tion time of the spectrometer was chosen to reduce the noise of
each individual spectrum. Then averaging of individual spectrum
is completed to improve the signal to noise ratio. The area under
the curve is determined by the trapezoidal method, which intro-
duces negligible error due to the adequately ne resolution of
the spectrometer. Therefore the experimental scatter shown in
Fig. 7 should be understood as an inherent limitation of the tech-
nique, arising from the stochastic nature of spark generation in
gases.
4. Conclusions
Spectra from electrical and laser sparks in owing methaneair
mixtures of various compositions have been collected and ana-
lysed. The spectrum from electrical spark shows the best signal
to noise ratio. However it suffers from large broadband emission.
Thus data are difcult to analyse and the accuracy is deteriorated.
To prevent broadband emission it may be better to work with low
spark frequency. On the contrary, laser spark emission has very lit-
tle background emission which makes LIBS a more accurate tech-
nique than SIBS to measure hydrocarbon concentration. The
spectral region between 370 and 395 nm is the most sensitive to
the fuel concentration and hence for both ignition techniques, it
is found that the area under the broad CN* peak (around
388 nm) offers a signal that evolves linearly with fuel concentra-
tion. A LIBS technique using low-cost spectrometers seems to be
feasible.
Acknowledgements
We thank Prof. S.F. Ahmed of King Fahd Institute of Petroleum
for useful discussions on the electrical spark and its emission.
The origins of this work lie in preliminary experiments he did
while at the University of Cambridge.
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