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A Gas Chromatographic Method for Exhaust Gas

Analysis
a a a
A. Lamb , K. A. Larson & E. L. Tollefson
a
University of Calgary
Published online: 15 Mar 2012.

To cite this article: A. Lamb , K. A. Larson & E. L. Tollefson (1973) A Gas Chromatographic Method for Exhaust Gas
Analysis, Journal of the Air Pollution Control Association, 23:3, 200-202, DOI: 10.1080/00022470.1973.10469766

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 A Gas Chromatographic Method for
Exhaust Gas Analysis
Downloaded by [Illinois Wesleyan University] at 04:44 09 October 2014

A. Lamb, K. A. Larson and E. L. Tollefson

University of Calgary

A gas chromatographic method is described which may be applied in the analysis system using two thermal conductivity
of stack and exhaust gases. Two separate columns each containing sections of detectors to separate HC, NO, NO2,
CO, 02, and N2. Frazer and Ernst2
Porapqk Q and R are used. The first is held at — 78°C until carbon monoxide also developed a multicolumn system
elutes, then is programmed to room temperature. This column separates H2, N2, which separated hydrocarbons, N2,
O2, A, CO, NO, CH4, CO2 and N2O. The second, maintained at 160°C, separates NO, CO, and CO2 using a thermal
hydrocarbons up to and including hexane but not NO2 directly. Water can be conductivity detector at 50-60° C.
removed at the beginning of the second column by a short section containing cal- Bennet3 used a combination of Porapak
Q and molecular sieve 5A to separate
cium sulfate placed ahead of the main column packing. Applications of the O2, N2, NO, CO2, and methane. Mallik
analytical method in the analysis of automobile exhaust gases and in the study and Khurana4 used the same column
of the catalytic reduction of oxides of nitrogen are discussed. combination as Bennet3 combined with
thermal conductivity and flame ioniza-
tion detectors to analyze for CO, CO2,
HC, and water.
The use of silica gel in the analysis
of low concentrations of NO and NO2
is reported5.6 but special column treat-
ment is required because of tbs revers-
ible adsorption of these oxides of nitro-
Oxides of nitrogen play an important The analytical method proposed is gen.
role in the complex atmospheric reac- simple, involving one gas chromato- Cleemput7 describes a three-column
tions which may ultimately result in the graph incorporating a thermal conduc- system (Carbowax on glass beads,
formation of photochemical smog. tivity detector and two pairs of gas Porapak Q, and molecular sieve) and
Sources of oxides of nitrogen can be chromatographic columns. Increased a single thermal conductivity detector
classified as being either mobile or sensitivity towards hydrocarbons may that was claimed to separate O2, N?,
stationary. Examples of such sources be obtained by the use of a hydrogen CO2, NO, N2O, and NO2. These were
are the automobile exhaust and stack flame detection system. retained in the first column (Carbowax)
gas from a nitric acid plant. by immersion in liquid air. Subsequent
This paper is concerned with the anal- Review of Gas Chromatographic Methods immersion in boiling water after the
ysis of certain components of such emis- Complex gas chromatographic sys- P2 and N2 were eluted from the molec-
sions including oxygen, nitrogen, nitro- tems have been developed to analyze ular sieve column enabled CO2, NO,
gen dioxide, nitric oxide, carbon monox- for hydrocarbons (HC) and oxides of N2O, and supposedly NO2 to be sepa-
ide and simple hydrocarbons up to nitrogen present in the same sample. rated by the Porapak Q at room tempera-
and including hexane. Trowell1 developed a three-column ture. f

200 Journal of the Air Pollution Control Association

 Bethea and Meader8 in their recent
review of gas chromatographic methods
for the analysis of reactive gases in air
stated that no single column was avail-
able which would separate NO, NO2,
SO2, HC1, H2S, Cl2, NH3, as well as
H2O and CO2. These authors further
point out that the best separation of
nitric oxide and air was made on the
combination column described by Wil-
hite and Hollis.9
Wilhite and Hollis9 found that 8 ft of
50-80 mesh Porapak Q in series with
8 ft of 50-80 mesh Porapak R gave
separation of H2, N2, NO, CH4, CO2,
NO2, and H2O when temperature pro-
grammed from 25 to 150°C. O2, A,
and CO were found combined as a sin-
gle peak. Trowell,10 however, in a
recent paper, points out that NO2
reacts with Porapak Q to give NO,
H2O, and nitration products of the Pora-
pak Q. Thus the NO2 reported by Wil-
Downloaded by [Illinois Wesleyan University] at 04:44 09 October 2014
hite and Hollis9 and by Cleemput7
was probably water. Trowell10 also
found that the water produced from this
reaction exhibited a retention time dif-
ferent from that of water injected into
the column.
Experimental
Two gas chromatographic columns
were prepared:
Column 1—consisted of 10 ft of
Porapak Q, 50-80 mesh, in series with
5 ft of Porapak R, 100-120 mesh, in
% in. I.D. teflon tubing.
Column %—consisted of 1 in. of cal- — 78°C for 15 min. An immersion time
cium sulphate in series with 10 ft of
Porapak Q, 50-80 mesh, and 5 ft of
Porapak R, 100-120 mesh, in y% in.
I.D. teflon tubing.
A Varian Aerograph Model 1700 gas
chromatograph incorporating a thermal
conductivity detector was used for the
analysis. A 200° C detector tempera-
ture and 200 m.a. detector current were
maintained for the analyses. The sam-
ple size was 150 jul. (microliters). The
detection limit for nitric oxide was esti-
mated to be of the order of 0.01% but
this depends on sample size.
Column 1 was immersed in a dry ice-
acetone bath for approximately 15
min, after which time the sample was
injected into the column. The column
was maintained at — 78° C until the
CO was eluted (approximately 15 min
after sample injection), then removed
from the dry ice-acetone bath and al-
lowed to reach room temperature.
Methane and all inorganic components
except NH3, NO2, and H2O were ob-
tained from the analysis using this
column.
Column 2 was maintained at 160°C
for the duration of the analysis, (a
period of approximately 1 hr). The
analysis of hydrocarbon components
including methane was performed on
this column. Ammonia analysis was
not possible on this column.
March 1973 Volume 23, No. 3
Table I. Retention data column 1."
Retention
time
Component (minutes)
Hydrogen (H2) 3.0
Nitrogen (N2) 9.5
Oxygen (O2) 11.3
Argon (A) 12.5
Carbon monoxide (CO) 14.5
Nitrjc oxide (NO) 18.8
Methane (CH4) 25.5
Carbon dioxide (CO2) 35.0
Nitrous oxide (N2O) 38.4
a
Column 1: 10 ft of Porapak Q, 50-80
mesh in series with 5 ft of Porapak R, 100-120
mesh in )4 in. I.D. teflon tubing.
Results and Discussion
Column 1 gave excellent separation
of O2, CO, and A, a separation which
was not possible using the method of
Wilhite and Hollis.9 Relative reten-
tion times are given in Table I and a
typical chromatogram is illustrated
in Figure 1.
These separations suggest that this
column (1) could be used with great
facility in the study of NO reduction
by H2 or CO and in the study of the
formation of nitrous oxide (N2O) as
an intermediate in the reduction process.
Table I shows this intermediate has a
retention time of 38.4 min.
The initial treatment of column 1
prior to sample injection was to immerse
the column in a dry ice-acetone bath at
less than 15 min resulted in poor separa-
tion of the gaseous components in the
sample. After this period of time the
sample was injected and the column
retained in the dry ice-acetone bath
until the CO was eluted. If the column
were removed from the bath prior to
CO elution, both CO and NO were ob-
tained as a single peak. When the
(Attenuations given in brackets)
0 3 4 11 12 13 14 15 16 17 18 21 22 23
Retention time (min)
Figure 1. Automobile exhaust analysis—Column 1.
column was retained at — 78° C for
approximately 20 min after CO elu-
tion, the total analysis time was an
hour or more. It was found that a
15-min period in the bath for cooling
the column to — 78° C and removal of
the column into the air after CO was
eluted gave adequate separations and a
scan of reasonable length.
The separation of gases containing
aliphatic hydrocarbons up to and in-
cluding hexane is illustrated by the
retention time data given in Table II.
These data are mainly based on single
component samples and therefore
separation of some of them may be dif-
ficult. For example, in automobile
exhaust containing approximately 12%
CO2, ethylene and acetylene could not
be determined at the low ppm level.
It is important to note that most of
components resolved on column 1
are eluted as a single peak labelled "air"
using column 2. CO2 and N2O have
equal retention times on column 2.
This is not an analytical problem since
these components are resolved on
column 1.
The problems associated with the
separation of NO2 and H2O discussed
by Trowell10 were also encountered.
The former could not be separated but
the latter was completely removed by
the use of a short (1 in.) column of
calcium sulfate at the front of column 2.
Further work on the reaction of NO2
with the Porapak Q/Porapak R column
system showed approximately 4% NO2
appeared as H2O at 125°C and 14%
at 165°C. There was an approximately
linear relationship between the NO2
injected and the quantity of water
eluted. Investigations were over a
column temperature range from — 78° C
to +165°C and H2O, the only com-
ponent eluted in significant quantities,
was only detectable above 100°C.
31 39 40 41
201
 Table II. Retention data column 2.a
Retention
time
Component (minutes)
Air(H 2 , N2, O2,A, CO, NO)
Methane
CO2 + N2O
Ethylene
Acetylene
Waterb
Ethane
Propylene
Propane
Butene-1
Trans-butene-2
Butadiene 1,3
Isobutane
Cis-butene-2
n-butane
iso-pentane
n-hexane
a
Column 2: 1 in. of calcium sulfate, 8 ft
of Porapak Q 60-80 mesh, 8 ft of Porapak R,
50-80 mesh in % in. I.D. teflon tubing.
b
From reaction of NO2 with packing.
Downloaded by [Illinois Wesleyan University] at 04:44 09 October 2014
The sensitivity of the thermal con-
ductivity detector was such that a
0.5 ml sample of 0.2% NO2 would
give a H2O peak height of 4 mm on
xl attenuation. A possible method for
analyzing NO2 by monitoring the H2O
produced is therefore indicated provided
any H2O contained in the sample is
removed by means of a short calcium
sulphate column at the front of the
column system.
Tables I and II show that the ana-
lytical method described would be useful
in the analysis of automobile exhaust
since nitrogen (the principal component)
can easily be separated from CO and
NO on column 1 and hydrocarbons can
be separated on column 2. Two sepa-
rate analyses of a single sample of auto-
mobile exhaust are shown in Figures
1 and 2. These are drawings of actual
chromatograms reduced in size.
No NO peak is shown in Figure 1
because none was detected on account
of the small sample size and the low
concentration present. (The sample
was collected from a cold engine under
4 5
Figure 2. Automobile exhaust analysis—Column 2.
202
conditions in which relatively little
NO is formed.) The relative position
of NO on the chromatogram and the
ease of separation of CO, NO, and N2
on column 1 are apparent.
2.6
2.7 Further examination of Table I
3.0 shows that this method is a useful
3.1
3.3
analytical tool in the analysis of systems
3.4
4.1
in which the reduction of NO by H2 or
CO is studied. The type of gas chroma-
5.1 tograph scan which might be expected
6.3 in the reduction of NO by H 2 is given in
9.4
10.4 Figure 3. It will be observed that the
10.6 analysis time is quite short, eg. ap-
11.4 proximately 20 min.
11.4 Although in this experimental in-
12.4
24.8 vestigation separate samples were in-
52.0 jected into columns 1 and 2, a back-
flush arrangement would enable hydro-
carbons other than methane to be ana-
lyzed on column 2 after the analysis
of H2, N2, O2, A, CO, NO, CH4, CO2
and N2O on column 1. Where signifi-
cant concentrations of carbon monoxide,
hydrocarbons, and oxides of nitrogen
are present thermal conductivity detec-
tion may be used.
Conclusions
The combination of the column pack-
ings Porapak Q and R in a single column
can be used for partial gas chromato-
graphic analysis of the components of
automobile exhaust including hydro-
carbons, oxides of nitrogen (except
nitrogen dioxide which is detected in-
directly when present in sufficient quan-
tity) and carbon monoxide provided
two temperature regimes are used.
The analytical method can also be used
in the study of the reduction of oxides
of nitrogen by hydrogen or carbon
monoxide, a significant factor in the
analysis being the ease of separation
of nitrogen, carbon monoxide, and nitric
oxide.
Acknowledgment
The assistance of L. A. Dornan with
some of the gas chromatographic anal-
yses is gratefully acknowledged.
(Attenuations given in brackets)
10 15 20 25 30
Retention time (min)
Journal of the Air Pollution Control Association
Column 1 (-78°C)
Attenuations in brackets (xl)
—
.Nitri
oxid
ogen
a> I
•o
QO
o E
o
ft
t> x
fl
-Nit
•=•
.5 1fi
1
i II
1 M >
E
o
o>
cn
I
t T"
LEII ?J|
i i
10 15 20
Retention time (min)
Figure 3. Analysis of the reduction products ot
nitric oxide.
References
1. J. M. Trowell, "Gas chromatographic
separation of oxides of nitrogen,"
Anal. Chem. 37: 1152 (1965).
2. J. W. Frazer and K. Ernst, "Chemical
reactivity testing of explosives," Ex-
plosivstoffe 12: 4 (1964).
3. D. Bennet, "Analysis of gas mixtures
by G. C.," / . Chromatog. 26: 482
(1967).
4. K. C. Mallik and M. L. Khurana, "A
dual column gas chromatographic
method for the analysis of automotive
engine exhaust gases," Anal. Chem.
(Berlin) 253: 125 (1971).
5. M. Fossard, R. G. Rinker and W. H.
Corcoran, "Determination of small
quantities of nitric oxide and nitrogen
dioxide in nitrogen by gas chroma-
tography," Am. Soc. Testing Mater.
Spec. Tech. Publ. 352: 56 (1963).
6. R. R. Sakaida, R. G. Rinker, R. F.
Cuff el and W. H. Corcoran, "Deter-
mination of nitric oxide in a nitric
oxide-nitrogen system by gas chroma-
tography," Anal. Chem. 33: 32 (1961).
7. O. V. Cleemput, "Gas chromatogra-
phy of gases emanating from the soil
atmosphere," / . Chromatog. 45: 315
(1969).
8. R. M. Bethea and M. C. Meador,
"Gas chromatographic analysis of re-
active gases in air," / . Chromatog. Sci.
7:655(1969).
9. W. F. Wilhite and O. L. Hollis, "The
use of porous-polymer heads for
analysis of the Martian atmosphere,"
/ . Gas Chromatog. 6: 84 (1968).
10. J. M. Trowell, "Reaction of nitrogen
dioxide with Porapak Q", / . Chroma-
tog. Sci. 9:253 (1971).
Messrs. Lamb, Larson, and Tol-
lefson are associated with the De-
partment of Chemical Engineering,
University of Calgary, 2920 24 Ave.
N.W., Calgary, Alberta, Canada
T2N 1N4.