GAS CHROMATOGRAPHIC ANALYSIS OF MIXTURES

CONTAINING OXYGEN, NITROGEN, AND

CARBON DIOXIDE
Nathaniel Brenner and Edward Cieplinski
The Perkin-Elmer Corpmarion, Norwdk, Conn.
The versatility and latitude of gas chromatography have increased rapidly
in the short years of its history. However, as is often true of rapidly develop-
ing analytical techniques, small obstacles to progress are often bypassed rather
than overcome. This is illustrated by the application of the technique to
the separation of samples containing oxygen, nitrogen, and carbon dioxide.
While most conceivable light gas separations had been accomplished by the
early workers who then proceeded to separations of much greater challenge,
this single, but significant, separation remained unaccomplished.
The use of solid adsorbents such as silica, alumina, and charcoal for the
separation of COZ from the other components of air is well documented.
The oxygen is separable from the nitrogen only incompletely and at such a
greatly reduced temperature (that of liquid nitrogen) that the time required
for elution of COn is excessive.
The problem of separating oxygen from nitrogen is considerably more difii-
cult. To date only one type of adsorbent has been reported that will perform
this separation adequately and conveniently. These are the synthetic zeolites
sold commercially under the name molecular sieves.* These materials suc-
ceed in making a complete and rapid separation of 0 2 and Nz at room, or even
elevated, temperatures. Other light gases such as methane, carbon monoxide,
and hydrogen also may be separated readily.
Unfortunately, all the molecular sieves developed to date adsorb carbon
dioxide irreversibly under those conditions necessary for separation of the
other light gases. Therefore, no sample to be analyzed for 02 and NZ content
could be analyzed concurrently for COZ content.
Therefore, all such analyses have been accomplished heretofore by two sepa-
rate analyses, at a consequent cost in time, equipment, and sample require-
ments.
The method described in this paper permits the analysis of all three gases,
plus other light gases of interest, using a single sample in a single analysis on a
standard gas chromatograph.
A parallel column system shown in FIGURE 1 was built to permit the pas-
sage of a portion of an injected gas sample into each of two flow paths a and
b. A column of SA molecular sieve was inserted in one part and a short col-
umn of silica gel (Davison type 15, 35 to 60 mesh) was placed in the other
part. Therefore, the portions of the sample were being separated in two
different modes. I n one, the separation was made into oxygen and nitrogen,
with COz adsorbed irreversibly. This separation alone is shown in FIGURE 2.
* Product of Linde Company, Division of Union Carbide & Carbon Corporation, New
York, N. Y.
705
706 Annals New York Academy of Sciences
I n the other column, a concurrent separation was made of the sample into
oxygen and nitrogen as one band and COZ as another. This separation is
shown in FIGURE 3. The combined separation performed by the parallel system
is shown in FIGURE 4.
The quantitative analysis of this system must be based upon the use of
known standards. The absolute amount of each component analyzed is de-
pendent not only upon its concentration in the sample, but is related also to
the relative flow impedances of the two columns a and b. For example, if the
silica has much larger particles than the molecular sieve and has a shorter
length or wider diameter, its resistance to flow will be much smaller. If this
is the case, a larger proportion of the sample will be swept into this column
along with the greater flow of carrier gas. Therefore, it will appear that a
relatively large quantity of COZ is present, although usually this is not the
case. I n practical use, the system very logically might be adjusted in this
way to increase the sensitivity to COr (usually present inlow concentrations)
vis & vis 0 2 and NZ (usually present in high concentrations).
However, provided that a single set of flow, temperature, and column con-
ditions is maintained, the division of the sample between the two columns
will remain at a fixed ratio. A convenient analogy may be made between this
FIGURE 1. Parallel column system.
Brenner & Cieplinski: 02, N2, and COz Mixtures 707
FIGURE 2. Expired air.
system and a system of parallel resistors in an electrical circuit.
tric analogue,
I n the elec-
- A\
3\ "_/'
\ M
+
Ri
the current I , passing through each of the 2 arms will be inversely proportional
to the ratio of the resistances RI / Rz regardless of the absolute value of I .
This is, of course, Kirchhoff's law.
The same condition of proportionality is attained in our pneumatic system.
Therefore, a second sample of gas injected into the instrument as a standard
708 Annals New York Academy of Sciences
FIGURE 3. Expired air.
will divide in the same volume ratio as did an unknown gas. Therefore, a
series of standards may be used to establish working curves of concentration
per unit height of each component band of interest. These curves may then
be used directly for immediate calculations of component concentration in
unknown mixtures:
Other light gases also may be analyzed together with the 0 2 , N2, and CO2
system. Carbon monoxide, cyclopropane, and ethylene, all of interest in
medical and physiological applications, may be analyzed conveniently. FIG-
URE S illustrates a separation of this type, cyclopropane being the component
added. The concentrations of components in this sample are shown in
Flows were adjusted to each column to give minimum time of elution for
cyclopropane and equal sensitivity requirements for COZ , Ca a , and 02.
TABLE 1.
B re inner & Cieplinski: 02, N2, and C0 2 Mixtures
FIGIJRE 4. Expired air. Ierkin-Elmer model 154-C.
709
FIGURE 5. Anesthesia mixture.
710 Annals New York Academy of Sciences
TABLE 1
Component
0 2
Per cent concentration
16
N,
coz
CaHs
64
5
15
The particular run shown here illustrates the reproducibility expected under
the least carefully controlled conditions: no thermostat was used to minimize
temperature fluctuations during the analyses. The cyclopropane peak may
be compared with that of an identical sample run previously (band at right).
Had a thermostat been employed, greater precision would be expected.
I n many applications, high speed of analysis is essential. Analytical time
may be reduced by several procedures: (1) operating the instrument at ele-
vated temperatures; (2) operating at elevated pressures; and (3) using shorter
columns of high efficiency. All of these variables may be applied within the
limits of resolution of the components of interest.
The result on the analysis time of an increase in pressure is shown in FIGURE
6 where the 0 2 , Nz , and COz time has been reduced to 2 min. from the 9
min. required originally.
The parallel column system theoretically may be extended in application to
FIGURE 6. Expired air.
Brenner & Cieplinski: 02, N2, and COZ Mixtures 711
FIGURE 7
any problem in which one column fails to provide complete separation, but
practically is limited to cases in which either few components are present or
(as in the case of molecular sieves) only a few components are eluted, others
being adsorbed.
The 02, NZ , and COZ separation in mixtures containing higher hydrocar-
bons may be considered. I n the mixtures containing no components above
Ca and no acetylenic components, the silica gel-molecular sieve system is still
useful. However, for higher hydrocarbons, a system of molecular sieve and
a partition column capable of separating those hydrocarbons as well as COs
is recommended.
FIGURE 7 illustrates a partial separation of 0 2 , Nz , and C1 to C4 paraffins
on the molecular sieve column. No peaks are recorded for ethane, propane,
or n-butane.
FIGURE 8 shows the result of running the same sample on a partition col-
umn. The complete separation
of all components by the parallel column system is shown in FIGURE 9.
02, NP , and methane are eluted as one band.
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Annals New York Academy of Sciences
FIGURE 8
FIGURE 9
Brenner & Cieplinski: O,, N,, and COz Mixtures
References
7 13
1. GKEENE, S. A., H. I,. MOBERC & E. M. WILSON. 1956. Separation of gases by gas ad-
sorption chromatography.
2. GKEENE, S. A. & H. PUST. Use of silica gel and alumina in gas-adsorption chro-
matography. Anal. Chem. 29: 1055.
3. J ANAK, J . 1958. Analysis of natural gas and determination of methane in nine gases.
Rept. NO. 13. Inst. Natl. Industrie Charbonnihre. Liege, Belgium.
4. COATES, V. J . & N. BRENNEH. 1956. Fuel gas analysis by gas chromatography. Petrol.
Refiner. 36(11): 197-201.
Anal. Chem. 28: 1369-1370.
1957.