ANALYTICAL

SCIENCES

FEBRUARY

Continuous
Analysis
Infrared
Spectroscopy
Minoru

1993, VOL.

of Vehicle

77

Exhaust

Gas by Fourier-Transform

ARAI

Isuzu Advanced

Engineering

Center, Ltd.,

Fujisawa,

Tsuchidana,

Kanagawa

252,

Japan

Fourier-transform infrared spectroscopy (FT-IR) was applied to a continuous measurement of unregulated emissions
from a diesel engine. Improvements in measuring the diesel exhaust gas were achieved by heating the gas sampling line,
adapting the filter to remove particles in the exhaust gas, and modifying the window material of the sampling cell. An
increase in the sample flow rate as well as a volume reduction of the sampling cell could improve the response of FT-IR,
though it was insufficient under transient conditions. It was confirmed that FT-IR could continuously and
simultaneously detect unregulated emissions, such as HCHO and NH3, as well as regulated emissions. The measured
concentration level of unregulated emissions was very low. It was suggested that FT-IR might be useful in estimating any
change in the combustion process by measuring the intermediate products, including HCN and HONG, which are related
to NO production during combustion. It was also demonstrated that gaseous unregulated emissions from vehicles can
be measured in real-time by FT-IR.
Keywords

Fourier-transform

infrared

spectroscopy,

The emission of exhaust gas from vehicles is regulated

in order to prevent air pollution; here, regulated emission
refers to nitrogen oxides (NOr), carbon monoxide (CO)
and the total hydrocarbon content (T. HC). An analyzer equipped with a specific detector is required for
measuring each objective emission component. Nitrogen oxides are analyzed using a chemiluminescence
analyzer (CLD); carbon monoxide is analyzed using a
nondispersive infrared analyzer (NDIR); and the total
hydrocarbon content is analyzed using a flame ionization
detector (FID), which is the same as that used for gas
chromatography.
These analyzers are widely used on
the vehicle production lines of factories, as well as in the
research and development of engines. Although a routine method for measuring those regulated emission
components has already been established, a more
versatile method used for the continuous determination
of vehicle exhaust emissions is needed in order to solve
both quantitative and qualitative problems concerning
unregulated emissions, which have not been understood
well. Unregulated emissions are, for example, sulfur
oxides, aldehydes and polycyclic aromatic hydrocarbon
(PAH). Although regulated exhaust emissions have
been reduced for many years, it is considered that
unregulated emissions will also be examined in the
future. Although analytical results concerning unregulated emissions have been reported in a few papers"2,
the analytical methods have not been established yet. In
case of the unregulated emissions, such as aldehyde and
ammonia, high-performance liquid chromatography3
and absorption photometry4 have been used to determine
these emissions. These conventional analytical meth-

diesel,

unregulated

emissions,

real-time

ods cannot continuously

determine
the emission values
for analytical studies.
The purpose of this study was to
evaluate and develope an analytical procedure
which can
continuously
analyze both regulated
and unregulated
emissions.
In recent years, Fourier-transform
infrared
spectrascopy
FT-IR,
which can simultaneously
determine many components
in real time, has been studied
regarding
the measurement
of unregulated
emissions.s,6
Though
the data obtained
from FT-IR
and the other
methods have a good correlation,
the correlation
data of
unregulated
emissions have almost been limited to those
on aldehydes.
The present paper describes
test results
concerning
both regulated
and unregulated
emissions of
formaldehyde
and the others by FT-IR.
The advantages of continuous
measurements
for analytical
studies
were confirmed,
and desirable
improvements
of FT-IR
for vehicle exhaust gas analysis described.

Experimental
A model REA FT-IR spectrometer
was manufactured
by Mattson.
It was modified
so as to be capable
of
sampling
and measuring
exhaust
gas from vehicles,
as
shown in Fig. 1. Since water vapor and particle resulting from fuel combustion
exist in exhaust
gas, the
sampling
system
was improved
to prevent
water
condensation
and contamination
by exhaust gas.
Water condensation
and
by heating
the sampling
in the sampling line.
The
line from the exhaust
tail

contamination
were avoided
line and adopting
a filter
temperature
of the sampling
pipe to the particle-remov-

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ANALYTICAL

Fig.

Sampling

line for measuring

ing filter was kept at 80 C. The section between the

filter and sample cell was controlled to be 60 C. The
temperature of the sample cell was maintained so as to be
higher than that at room temperature in order to avoid
the condensation of water. The window material was
changed in order to prevent deliquescence, and a multireflected sampling cell was used for gas analysis at a lower
concentration. The interferogram obtained from a
Michelson interferometer was changed to infrared
absorption spectra by the Fast Fourier Transform (FFT)
algorithm.' This algorithm is generally used for all
types of FT-IR. A quantitative analysis for multicomponents was carried out by resolving the absorption
spectrum to linear combinations of the characteristic
spectrum for each component. The concentration of
each component was corrected by solving simultaneous
equations in which each concentration was treated as a
variable. The coefficient for each component was
obtained by storing each absorption spectrum of known
concentration gas. Details concerning the FT-IR specification are listed in Table 1. Other conventional
analytical methods used to measure vehicle exhaust gas
were also used in order to make comparisons with FT-IR.

Table

the vehicle

FT-IR

SCIENCES

exhaust

FEBRUARY

1993, VOL.

gas.

specifications

Carbon monoxide, nitrogen oxides, and hydrocarbon

were analyzed by NDIRa, CLDb and FIDC, respectively
(HORIBA, AIA-120a, HORIBA, CLA-150Mb, HORIBA, FIA-125 ). The ranges for the measurement
of
each analyzer were 0 -100 ppm for carbon monoxide

ANALYTICAL

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FEBRUARY

1993, VOL.

79

Table

Fig.

FT-IR

Variation

of

the

CO2

concentrations

measured

Diluted

specifications

emission regulations.
The LA-4 test mode is shown at
the upper side of Figs. 2 and 3. Three types of fuel were
used for these emission tests: Fuel-A, Fuel-B and
Fuel-C (Fuel-C was of low sulfur content).
Test fuel
specifications are given in Table 2.

concentration

of NO 2 and NO measured

by

FT-IR.

and nitrogen
oxides, and 0 - 200 ppm for hydrocarbon.
The calibration
of each analyzer was conducted
by using
span
gases,
which
Chemical
Industry.

Fuel

by

and NDIR.

Results

Fig.

were
The

supplied
from
Takachiho
test vehicle
was a diesel-

powered passenger
car; the emission measurements
were
conducted
under the conditions
of simulated
road load
on a chassis dynamometer.
The modes of the emission
measurements
were three steady state modes and the LA4 test mode, which was designed
to satisfy the USA

and

Discussion

Absorption spectra obtained by FT IR

Fourier spectroscopic analysis has the great advantage
that it can be used to simultaneously analyze the entire
range of wavenumbers.
A quantitative
analysis of
multicomponents
can be conducted by resolving the
absorption spectrum through linear combinations of the
characteristic band for each component.
The spectrum
obtained from interferogram
involves the overlapped
spectrum of many components, which can be separated
by determining the wavenumbers of the peaks as well as
the intensities of the peaks in order to satisfy the actual
overlapped spectrum.
The absorption spectra of NO
were observed within the 1800 -1950 cm 1 range, and
those of NO2 were observed within the 1580 -1650 cm 1
and 2860 - 2940 cm' ranges.
For example, the absorption spectra of HCHO are presented in Fig. 4, in
which the absorption
spectra obtained by Fourier
transform shows the variation in their intensities within a
narrow range of wavenumbers.
FT-IR can resolve the
absorption spectra in detail, due to its high resolution, as
shown in this figure (resolution Av=0.5 cm 1). The
1680 -1800 cm 1 and 2700 - 2950 cm' ranges are considered to be the stretching modes of C=0 and CH,
respectively, in this absorption spectra of HCHO.
The
intensities of most of the components showed a variation
within a narrow range of wavenumbers, indicating that
many spectral modes, such as stretching, bending and
rotation, are involved in these absorption spectra.

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SCIENCES

flow rate is basically

IR response.

Fig.

Absorption

spectra

of aldehyde

from

the

interfero-

gram.

Response to a change of the exhaust-gas concentration

To investigate the output response when exhaust gas is
introduced, CO2 concentration in the exhaust was
measured by FT-IR and NDIR at 2500 rpm, the 100%
steady state load of the engine operating condition. The
output response is defined here as being the time required
to achieve a saturated output. The response of NDIR
was very quick, and the measured value became stable
within a few seconds, while the response of FT-IR was
much slower, and stable measured values were obtained
after 40 s. The long response time of FT-IR was
considered to be caused by the large volume of the sample
cell and the low sampling gas-flow rate, compared with
the cell volume. The diluted CO2 concentration was
simultaneously measured by FT-IR and NDIR while in
the LA-4 test mode, which was the simulated vehicle
running condition while changing the engine operating
conditions. The results are given in Fig. 2. NO was
also measured at a lower concentration level by FT-IR
and CLD, though the results are not shown. From
these test results, the FT-IR response was found to be
much slower than those of NDIR and CLD, indicating
that the peak variations obtained at lower concentrations
from FT-IR were considerably less than those from
NDIR and CLD, as shown in Fig. 2. The FT-IR
response is not sufficient for measurements while in the
transient state, which requires a fast response. Since it
is considered that the slow response is caused for the same
reason as that during the steady state, a small-volume
sample cell with a sufficient resolution and gas-sampling

needed

FEBRUARY

in order

1993, VOL.

to improve

the FT-

Characteristics of the NO and NO2 concentration in the

transient condition
The change in the NO concentration was quite different from that of NO2 while in the transient condition
during LA-4. A change in the NO concentration was
obviously observed to exist, while that of the NO2
concentration was small. The detection limits were
determined to be twice the noise level when no gas was
introduced; the noise level was defined as the root mean
square of the measured value at the time of gas. The
detection limits of NO and NO2 are 0.3 ppm under the
condition of 3 s/ scan, which was used for these tests.
The test results are given in Fig. 3. The change in the
NO2 concentration was not significant under either a
medium or light load of the engine operating conditions,
such as the LA-4 test mode. Although the characteristics of NO2 formation had not been well analyzed,
compared with those of NO and NO, the test results are
sufficient to determine the characteristics of NO2 formation in the test mode. This was also confirmed by NDIR
and CLD, in which NDIR was used for the NO
measurement, and CLD was used for NOR, i.e. practically
the total of NO and NO2. Since NO minus NO is NO2,
the NO and NO2 concentration can be obtained. Although NO and NO emissions are generally analyzed on
the basis of those emission characteristics in many cases,
NO2 has not been successfully analyzed. FT-IR could
be used to simultaneously detect these two components
of NO and NO2, and its advantage was confirmed.
Average concentration from the integrated value
FT-IR and NDIR were simultaneously used for a
continuous analysis of CO2 during the LA-4 test mode;
both concentrations were averaged for a comparison.
The average concentration during the analysis was
calculated by dividing the integrated concentration value
by the integrated time. The value from FT-IR was
about 79%, compared with that from the NDIR measurement. The insufficient output caused by the slow
response led to a lower average concentration.
Above
all, the gas peaks at higher concentrations were greatly
affected, as shown in Fig. 2. A continuous analysis of
NO was also conducted by FT-IR and CLD simultaneously. The average concentration of NO from
FT-IR was 84%, compared with that from the CLD
measurement. The cause of the lower average concentration was considered to be the same as that for CO2.
A slow response leads to lower concentrations than the
real ones, because the sample gas introduced in the
sample cell is swept away before the concentration can be
correctly indicated. It is thus desirable to improve the
slow response for measuring such components as
unregulated emissions, which cannot be detected by
other types of analyzers.

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1993, VOL.

Dependence of nitrogen compounds on the fuel specfiications

FT-IR has an ability to analyze intermediate products
which are produced during fuel combustion in an engine,
as well as the regulated and unregulated components.
Fuel-A tended to show a higher ratio of NO2/ NO than do
other fuel types in this study. However the concentrations of NO and NO2 generated from nitrogen in
the fuel were generally very low, and the nitrogen content
in Fuel-A was less than that of the other types of fuel.
Figure 5 shows this tendency; the nitrogen content is
shown in Table 2. As a result of these facts, NO2 could
not originate from nitrogen in the fuel. It is therefore
considered that fuel-A possesses a slightly lower combustion temperature, and the ratio of NO2 is increased.
Fuel-A also tends to produce a high concentration of
nitric compounds, such as HCN, HONO and NH3,
compared with that of other fuels (refer to Table 3).
From the viewpoint of combustion, the possible formation of these nitric compounds is considered to be due
to reactions related to the NO production processes.
These reactions are as follows:

Fig.

Generated

NO2 and NO under

operation.

Table

Test results

of Fuels

A,

1000 rpm

steady

state

81

CH2+N2-HCN+NH
HCN+OH-HCN+H2O
CN+02-*CO+NO.

NH+OH-N+H2O
orN+OH-*NO+H

Indeed,
Ohtake
et al.8 suggested
that these reactions
with a low activation
energy proceed
easily when the
flame temperature
is low in the diffusion
flame.
If
Fuel-A produces
a lower flame temperature,
a higher
concentration
of nitric compounds,
such as HCN, which
are intermediate
products
related with NO formation,
can be assumed.
The fact that Fuel-A produces
only a
slightly higher ratio of NO2 is considered
to be due to the
lower flame temperature.

Interpretation of the analytical results according to the fuel

types
The analytical results obtained by FT-IR are summarized in Table 3. Concerning unregulated emissions,
the variations in those emissions were not obviously
observed when the fuel was changed and the quantity was
very small. Only a small amount of NH3 was detected at
almost only 2500 rpm steady state for all of the fuel types.
The amounts of measured SO2 were almost directly
proportional to sulfur content in the fuel. This means
that sulfur dioxide is due to the oxidation of sulfur in the
fuel. Nitrogen compounds varied when the fuel was
changed; the results suggest that Fuel-A tends to produce
higher concentrations of nitrogen compounds due to the
lower flame temperature. A calibration of the output
for those components had been conducted by using
calibration gases, and the relation between the absorbance and the concentration of each component had been
stored in data memory. The ranges of the wavenumbers
used for determining the absorbance of some components were as follows: for SO2, 1320 -1400 cm1; for
NH3, 800 -1200 cm 1 and for HCN, 710 - 720 cm 1.
Those spectra reflected the high resolution of FT-IR,
which is based on precise wavenumbers, a high SN ratio,
and a precise absorbance measurement. In continuous
analysis using FT-IR, it was confirmed that the amounts
of unregulated components are very small, and that they
are slightly affected by the fuel specifications.

B and C under steady state operation (2500 rpm; unit: g h-1)

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The author
University
Ltd.
useful

would

like to acknowledge

for his useful

for their
for basic

assistance
surveys

suggestions,

Prof.

Inoue

and to thank

and the use of their

FT-IR,

of Keio

HORIBA,
which

is

and research.

References

1. D. Schuetzle, T. L. Riley, T. J. Prater, T. M. Harvey and

D. F. Hunt, Anal. Chem., 54, 265 (1982).
2. R. A. Hites and T. E. Jensen, Anal. Chem., 55, 594 (1983).
3. F. Lipair and S. J. Swarm, J. Chromatogr., 247, 297
(1982).
4. JIS K 0099, "Methods for Determination of Ammonia in
Exhaust Gas", Japanese Industrial Standards Committee,

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1993, VOL.

Tokyo, 1983.
5. D. Bianchi, J. L. Gass, C. Bouly and D. Maret, Society of
Automotive Engineers, Inc. Technical Paper Series
910839 (1991).
6. S. Kawarabayashi, Y. Yamagishi, H. Kachi and S .
Kobayashi, in "International Symposium COMODIA 90" ,
p. 365, Kyoto, 1990.
7. S. Tasumi, "Basis and Practice of FT IR", p. 55, Tokyo
Kagaku Doujin, Tokyo, 1986.
8. K. Ohtake and T. Fujiwara, "Combustion Engineering", p.
178, Coronasha, Tokyo, 1985.
(Received August 10, 1992)
(Accented October 30. 1992.1