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Kultur Dokumente
Department of Environmental and Industrial Health, University of Michigan, Ann Arbor, Michigan 48109
R i c h a r d D. S a c k s
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109
Reproduction (photocopying) of editorial content of this journal is prohibited without publisher's permission. 643
Journal of Chromatographic Science, Vol. 28, December 1990
by a continuous flow of cold nitrogen and was resistively heated nected to a short length of multistrand copper wire, which served
by a current pulse from a capacitor discharge power supply. as an electrical contact to allow resistance heating of the t r a p .
M o r e recently, van Es et al. described a fast G C system that The copper wire was wrapped tightly a r o u n d the trap tubing,
utilized a similar inlet (18). In their design, a 50-μm capillary soldered in place, and then covered with electrical tape. The
column was used for the separation. The upstream end of the power supply used to heat the t r a p for reinjection was similar
column was threaded through a larger diameter, aluminum clad to that described in an earlier publication (15). The design in
capillary, which served as the heating element. Their t r a p was cludes two circuits, a variable-voltage capacitor discharge system
also cooled by a flow of nitrogen gas and was heated by running for rapid heating and a transformer-based sustainer circuit that
a current from a transformer through the a l u m i n u m coating was used to prevent the trap from cooling too quickly. T h e
on the outer capillary. Using this system, the authors observed capacitor discharge system supplied a 10-20 msec pulse of up
initial b a n d widths as small as 1 m s . to 75 A at 35-75 V.
Although each of the previous designs was shown to produce
narrow injection b a n d s , most were not evaluated for use in Operating conditions and chromatographic equipment
routine analytical procedures, and in some cases they d o not All c h r o m a t o g r a m s were collected isothermally at column
appear to be practical for a wide range of applications. In this temperatures of 35-60°C from a 5-m × 0.25-mm i.d. fused-
report, we present the results from a systematic, quantitative silica column with a 0.1-μm b o n d e d methylsilicone stationary
evaluation of an improved cold trap inlet that may be useful phase (Quadrex). The carrier gas was hydrogen, which was sup
for reducing analysis times in m a n y routine applications. D a t a plied at a flow rate of 2.5–3 m L / m i n to produce linear velocities
concerning trapping efficiency for a variety of organics, trap of 1 4 – 1 7 5 c m / s . The injector and detector were heated to
heating characteristics, and chromatographic performances are 225°C. A Varian flame ionization detector was used in all ex
presented. T h e system described could be added to most periments. To minimize the effective dead volume, the column
capillary G C systems, and in m a n y cases it would allow the was moved close to the base of the flame.
analyst to shorten retention times without loss of resolution or Test mixtures were prepared either without solvent or in high-
reproducibility. purity C S provided by the Dow Chemical Company. The injec
2
tion volume was 2.5 (μL in all cases, and the split ratio ranged
from about 50:1 to 500:1 depending on the sample concentration.
Experimental
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Journal of Chromatographic Science, Vol. 28, December 1990
C h r o m a t o g r a p h i c d a t a were collected at frequencies ranging then made with trapping and reinjection at various trap tempera
from 200 to 400 H z , depending on the peak width. A custom- tures, and the peak areas were compared to those obtained
built electrometer-amplifier with a response time of 5 ms was without use of the cold t r a p . In addition to comparing peak
provided by H N U Systems. C o m p u t e r hardware included an areas obtained with and without trapping, the F I D response was
80286/287-based personal computer a n d a D a t a Translation monitored during the entire process to allow any breakthrough
DT2801 analog-to-digital converter. D a t a acquisition was con of the sample to be detected. Because the sample concentra
trolled by using Labtech Notebook (Laboratory Technologies), tions were very high, even a small a m o u n t of b r e a k t h r o u g h
a n d the d a t a was analyzed with software developed in our could be noticed.
laboratory. Figure 2 presents an example of the results obtained during
Trap temperatures were measured with 36 gauge type J ther a trapping experiment performed with a mixture of seven
mocouples (Omega) spot welded to the approximate center of aromatics. The initial syringe injection was m a d e at the time
the t r a p tubing. T h e thermocouple o u t p u t was amplified with m a r k e d zero, and the t r a p heater was triggered at 40 s. Tracing
a high-speed differential amplifier built in-house and was then D was obtained without cooling the trap a n d shows the chro
directed to the analog-to-digital converter and sampled at 500 Hz. matogram that would be obtained with zero trapping efficiency.
Tracing C shows the c h r o m a t o g r a m obtained when the t r a p
temperature was dropped to 0°C. The sample was not efficiently
trapped, but there was a noticeable deterioration of the initial
Results and Discussion
c h r o m a t o g r a m . Tracing Β shows the c h r o m a t o g r a m obtained
Design considerations with a trapping temperature of — 50°C. Under these conditions
A n u m b e r of design considerations were found t o be impor the sample was partially retained, producing a general elevation
tant in determining the durability a n d performance of the of the base line. W h e n the heater was triggered, the trapped
system. T h e quality of the electrical contacts is especially im portion of the sample was reinjected to produce the c h r o m a t o
p o r t a n t in determining trap life. In order to provide a low- gram that starts at about 45 s. Tracing A shows the chromatogram
resistance electrical pathway, the contacts should cover as large obtained when the trap was cooled to — 100°C. At temperatures
a surface area as possible. It is also important that the trap this cold or colder, trapping was quantitative with recoveries
tubing not be held too rigidly, or mechanical stresses caused of 100% and n o detectable b r e a k t h r o u g h . The c h r o m a t o g r a m
by temperature-related length changes will tend to shorten the produced by reinjection under these conditions is therefore com
trap life. A standard injector septum with a small hole through parable to that shown in Tracing D .
the center was found to provide a good seal at the end of the
cold trap without holding the tube too tightly.
The choice of trap material and dimensions also affects
durability and reinjection performance. A n ideal material would
have high electrical resistivity, low chemical activity, and a low
coefficient of thermal expansion; would be highly malleable;
and would not work-harden. A number of materials, including
stainless steel, nickel, platinum, Monel 400, and an alloy of 3 0 %
c o p p e r - 7 0 % nickel, were evaluated for use as t r a p tubes.
Although platinum appeared to have the most desirable charac
teristics, the cost was considered prohibitive, a n d the work
reported here was done with a trap made of Monel 400. Stainless
steel, which was used in some early studies (14,15), is the least
expensive and most readily available material. However, it is
the least desirable choice because of its tendency to work-harden
and become brittle.
Another factor affecting trap durability and performance is
the wall thickness of the t r a p tubing. Increasing wall thickness
will obviously increase the strength and durability, but the
decreased electrical resistivity and increased thermal mass make
rapid heating and cooling m o r e difficult. For a t r a p m a d e of
hard-tempered Monel 400 with an internal diameter of 0.25 m m ,
a wall thickness of 0.18 m m provided a good combination of
strength a n d performance.
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Journal of Chromatographic Science, Vol. 28, December 1990
Trapping efficiencies for a n u m b e r of c o m p o u n d s that are However, for materials with boiling points similar to those used
important in environmental monitoring or in industry are here, trapping efficiencies were greater t h a n 9 0 % .
presented in Table I. At temperatures of - 100°C or colder, each Along with the choice of test materials, the duration of the
of the tested compounds was effectively trapped and reinjected. trapping cycle may also be an i m p o r t a n t consideration. In the
A p p a r e n t trapping efficiencies of greater t h a n 100% are at application described here, the trapping cycle normally lasts only
tributed to a transient decrease in the split ratio caused by con 5–10 s so any slow loss of the trapped material will be negligible.
densation of the sample in the cold t r a p . These variations in The overall efficiency of the cold trap as a high-speed injection
trapping efficiency for different compounds may introduce some system is also dependent o n how fast the sample can be reva-
error during quantitative analysis of liquid mixtures with split porized a n d o n the stability of the sample during the trapping
injection. This effect has been described by other authors (23) and reinjection process. Figure 3 shows the t r a p temperature
and can be eliminated by using a similar system with a gas samp during heating cycles that were initiated at various reinjection
ling loop a n d n o splitter. As discussed in the following section, voltages. Each data point on the graph represents the average
peak area reproducibility for replicate injections was very good, reading from five heating cycles and has a relative standard
with coefficients of variation ranging from 1 to 5 % or less in deviation of less than ± 10°C. Some of the early d a t a points
all cases. are missing because of interference from the initial discharge
In addition to the results presented in Table I, trapping effi of the capacitors. This problem became m o r e severe at higher
ciency was also measured for 1 % solutions of aromatics pre voltages.
pared in C S . T h e trapping efficiencies obtained in those ex
2 At an initial capacitor charge of 40 V (D), the t r a p tempera
periments were not significantly different t h a n those measured ture increased from — 170°C t o a peak of - 50°C in a b o u t
without solvent. 12 ms. Charging the capacitors to a higher initial voltage resulted
As indicated by the data presented in Table I, m a n y materials in b o t h faster heating and higher m a x i m u m temperatures. A t
can be effectively trapped and reinjected at - 100°C. However, an initial charge level of 55 V (A), the t r a p reached a peak
trapping behavior is not easily predicted on the basis of boiling temperature of nearly 200°C in a b o u t 20 m s .
point or freezing point, and in most cases an effective tempera The effect of capacitor charge on reinjection efficiency was
ture must be experimentally determined for each type of sample. also investigated for those c o m p o u n d s listed in Table I. The
Highly volatile materials, which may be gases at r o o m tempera results indicate that, for the materials used in these tests, max
ture, a n d low-volatility materials, which may be difficult to imum efficiency was achieved at voltages of 50–55 V, which cor
revaporize, have not yet been tested and may be difficult to trap responds to peak temperatures of a b o u t 150–200°C. As ex
and reinject with this system. pected, reinjection at lower voltages results in wider peaks and
In a similar test, G r a y d o n (22), using open tubular traps may not vaporize the less volatile components of the mixture
operated at liquid nitrogen temperatures, reported trapping being analyzed. This selective vaporization of less volatile com
efficiencies as low as 14% for some highly volatile c o m p o u n d s . ponents may present a problem for some separations. However,
it could also be useful in cases where the operator wishes to
analyze trace levels of a highly volatile component with minimal
T a b l e I. T r a p p i n g a n d R e i n j e c t i o n E f f i c i e n c y f o r interference from a less volatile solvent or from other com
2 3 C o m p o u n d s T e s t e d at T h r e e Different Trapping ponents of the sample.
Temperatures*
Efficiency (%)
Trapping temperature
Boiling Melting (°C)
Compound point (°C) point (°C) -50 -100 -150
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Journal of Chromatographic Science, Vol. 28, December 1990
If reinjection voltage is increased above 60 V, recovery effi reinjected with a 55-V pulse. Tracing Β represents the chro
ciency tends to decrease. At these higher reinjection voltages, m a t o g r a m obtained with syringe injection and n o cooling of
trap temperatures can rise to 350°C or hotter. Under these con the t r a p . Although the sample moves through the trap system
ditions, late-eluting peaks often become smaller as new, early- under these conditions, the use of low-dead-volume unions and
eluting peaks appear. This is apparently caused by pyrolysis of trap tubing that matches the internal diameter of the column
the larger molecules. Even for more stable compounds, recovery minimizes peak broadening in that area. Removal of the t r a p
efficiency may decrease at higher voltages. This is believed to tubing was found to produce n o improvement in performance
occur because rapid expansion of gases during the heating cycle for the n o n t r a p p e d samples.
increases pressure in the t r a p tubing a n d forces some of the As Figure 4 illustrates, trapping and reinjection produces
sample to flow backwards into the splitter. This effect was more noticeably sharper peaks and an improvement in resolution. The
dramatic in earlier designs t h a t used a shorter transfer line retention times for the four major peaks shown in tracing A
between the splitter a n d cold t r a p . are 5.98 s, benzene; 6.54 s, toluene; 7.33 s, chlorobenzene; and
Because the thermocouple response m a y involve a signficant 8.07 s, m-xylene. For benzene, cold trapping reduced the peak
lag, the true heating rate m a y actually be faster t h a n that in width at half height from a b o u t 230 ms to 75 m s . T h e number
dicated. T h e cooling rate, however, was slow relative to ther of effective theoretical plates for m-xylene was increased from
mocouple response times, so peak temperature measurements a b o u t 50 for the u n t r a p p e d sample to 2500 for the trapped
are thought to be accurate. Despite the response lag inherent sample. Although the improvement is clearly demonstrated in
in thermocouple-based temperature measurements, the data this example, the effect is even m o r e dramatic when retention
presented here indicate that the t r a p does heat quickly enough times are shorter and when conditions are optimized for speed.
to produce injection bands with widths of 20 ms or less, which To test the system repeatability, a series of 24 replicate
is adequate for rapid analysis on a 0.25-mm column. c h r o m a t o g r a m s was run over a 90-min time period using the
same mixture of benzene, toluene, chlorobenzene, and m-xylene.
Chromatographic performance T h e coefficients of variation for peak areas measured with and
The effect of cold trapping on the separation of a test mixture without use of the cold trap are presented in Table II. These
containing benzene, toluene, chlorobenzene, and m-xylene is data indicate that the cold trap introduces no significant increase
illustrated in Figure 4. Tracing A shows a c h r o m a t o g r a m ob in variability for peak area. In fact, for some separations, the
tained when the injected sample was trapped at - 100°C and improved peak shape and resolution may result in less integra
tion error and improved repeatability.
While retention time is not considered a reliable identifica
tion tool in the analysis of u n k n o w n mixtures, it is often useful
in applications involving routine or repetitive analysis of samples
from a known source. Using the computer-controlled high-speed
inlet, standard deviations of less than 0.01 s were recorded for
retention times ranging from 5 to 10 s.
Although the system described here should be considered a
prototype, this study indicates that it can significantly improve
the injection b a n d widths produced by a conventional capillary
inlet system. The smaller injection band produced by the cold
trap inlet improves chromatographic performance and increases
the n u m b e r of available plates for retention times of less than
10–15 s. By using a cold trap inlet similar to the one described
here with a G C system optimized for speed, it may be possible
to signficantly reduce retention times without loss of chromato
graphic quality. For some routine, repetitive applications this
could result in a reduced sample turnaround time and in signifi
cant cost savings.
Acknowledgments
T a b l e I I . C o e f f i c i e n t s of V a r i a t i o n f o r P e a k A r e a s
Measured from Chromatograms Made With and
Without the Cold Trap
Chloro-
Benzene Toluene benzene α-Xylene
Figure 4. Sample chromatograms made with and without the cold trap. With trapping 2.4% 1.8% 1.9% 1.5%
Conditions: (A) sample was trapped at—100°C and reinjected with a (n = 24)
55-V pulse and (B) syringe injection without cold trapping. Peaks: (1) Without trapping 1.6% 1.5% 1.9% 7.3%
benzene, (2) toluene, (3) chlorotoluene, and (4) m-xylene. (n = 8)
647
Journal of Chromatographic Science, Vol. 28, December 1990
assistance in the development of the capacitor discharge power 10. R. Annino and J. Leone. The use of coanda wall attachment fluidic
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in high-speed capillary gas chromatography. J. Chromatogr. 279:
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Journal of Chromatographic Science, Vol. 2 8 , December 1990
Atlas of Chromatograms
Organotin C o m p o u n d s a n d T u n g s t e n Tin C o m p l e x e s
LC126 and LC127 are reproduced by permission of Dr. Chris Dewaele of Bio-Rad R S L N.V. (Begoniastraat 5, B-9731 Eke, Belqium)
Atlas Consultant: Leslie S. Ettre.
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Journal of Chromatographic Science, Vol. 28, December 1990
Atlas of Chromatograms
S F C 9 6 is reproduced by permission of Christine Rouse and M.L. Lee, Brigham Young University (Department of Chemistry, Provo, U T 84602) and SFC97 is reproduced by permission o1
Frank Yang, Dionex Corporation (1228 Titan Way, Sunnyvale, CA 94086).
650