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GC connections

LCGC Europe - November 2001

Pneumatic Problems
John V. Hinshaw, ChromSource, Franklin, Tennessee, USA. Carrier-gas control is an essential feature of all gas chromatographs. Electronic pneumatic controls generally deliver the best carrier-gas control and engender more flexibility than traditional manual controls. In a previous GC Connections instalment, John Hinshaw addressed the degree of inlet pressure control required to produce a desired level of retention-time repeatability. In this months instalment, he explains how combining certain column dimensions and electronic pneumatic settings can produce unexpected behaviours that may surprise some unsuspecting chromatographers.

Modern electronic pneumatic systems for gas chromatographs deliver carrier and detector gases with unparalleled precision and accuracy compared with more traditional manual pneumatic controls. Chromatographers can program electronic pneumatic systems to maintain constant inlet pressure, constant column mass flow, or constant average carrier-gas linear velocity as the oven temperature changes (1). Keyboard control of split flow and ratio plus detector gas flow-rates are standard electronic pneumatic features that analysts expect. Electronic pneumatic systems facilitate new sampling modes, and they compensate for the effects of drifting ambient temperatures and atmospheric and column-outlet pressure changes. Operators must set the correct column dimensions, carrier-gas type and operating modes for electronic pneumatic systems to function at their full potential. Incorrect settings will produce unpredictable pneumatic behaviour. The computerprogramming aphorism, Garbage in, garbage out, certainly holds true for gas chromatography (GC) electronic pneumatic systems. Yet, even when correctly set, certain combinations of column type and pneumatic conditions can produce erratic behaviours that astute gas chromatographers can avoid. Before addressing these issues, I would like to discuss another concern about carrier gas that a reader, who chose to remain anonymous, posted on the on-line Chromatography Forum GC discussion at http://www.chromforum.com, in

response to the GC Connections instalment titled Off-Duty Columns, which appeared in the November 2000 issue of LCGC Europe (2). Off-Duty Columns Reader: I have a comment about the GC Connections column, Off-Duty Columns (2). The text states: First, cool the instrument but leave the carrier gas flowing. Next, remove the column from the detector and carefully insert the free end into a septum. Then, remove the inlet end of the column and insert it into the same septum. Residual carrier-gas pressure will maintain a positive flow out of the inlet of the column long enough to place it in the septum. Never store columns with one or both ends open because columns will trap atmospheric contaminants very efficiently, creating a column contamination problem upon subsequent use. I agree with this practice; however, if the carrier gas is helium, then this technique is not usable. If a helium-filled column is flame-sealed at both ends, then a total vacuum will be created in the column within 7 h. When sealed with a septum, the column will trap atmospheric contaminants and air. The pores of the fused-silica wall are approximately 2.3 in diameter; helium has a diameter of approximately 1.9 , which means that helium can penetrate through these pores quickly. On the other hand, hydrogen gas can also penetrate

through the fused-silica wall at a higher temperature. At room temperatures, this migration will occur very slowly, but after 24 h at 100 C roughly 60% of the hydrogen will have penetrated the column wall, leading to a vacuum and, if the ends are not flame-sealed, trapping of atmospheric contaminants in the column. Hinshaw: You are quite correct that helium diffuses through fused silica. This fact may surprise many chromatographers, but the effect was studied recently and reported in the Journal of High Resolution Chromatography in an article titled Effects of Permeation of Helium through the Walls of Fused Silica Capillary GC Columns by J.E. Cahill and D.H. Tracy (3). The authors describe observing lower-than-expected average carrier-gas velocities for helium at temperatures greater than 200 C, which was attributable to helium diffusion through the column walls. Nitrogen did not exhibit similar losses experimentally. Helium losses were generally less than 15% under the conditions usually selected for capillary column GC during the relatively brief time the carrier gas requires to transit a column in operation. The diffusion rate for helium at room temperature is approximately 35-fold less than it is at 250 C, according to the data presented in the CahillTracy article, and it is possible that most of the helium in a sealed fused-silica column will diffuse out of the column in less than one day. The authors cite a diffusion rate for hydrogen that is approximately 10-fold

LCGC Europe - November 2001

GC connections

less than helium, so some hydrogen loss also seems possible during extended column storage periods. The cautionary statement I made concerning contamination from the atmosphere is related to leaving one or both column ends open for long periods, however, in contrast to sealing the ends. Atmospheric contaminants will diffuse continuously a short distance into the open ends of a column and become trapped in the stationary phase. This absorption process effectively produces a positive flow of atmospheric contaminants into the column, which is limited by the contaminants diffusion rates. If I assume that the trapping process does not reduce the contaminant concentration in the surrounding air, then I can use a derivation of Ficks law to calculate the effective contaminant flow-rate into an open column end:
Fi DABAc Z [1]

where Fi is the effective contaminant flow-rate into the column; DAB is the contaminant diffusion coefficient in air; Ac, determined by 0.25 dc2, is the column entrance cross-sectional area; dc is the column inner diameter; and Z is the average distance that contaminant molecules diffuse into the column before being absorbed. Using 0.1 cm2/s for DAB, 0.053 cm for dc, and 0.1 cm for Z, the effective flow-rate into the column is 0.13 cm3/min. During a 20-day storage time approximately 500 h an air incursion of nearly 4 L would occur.

With both column ends sealed, the diffusion of atmospheric contaminants into the column ends will be nil. Although helium or hydrogen will diffuse from the column, no contaminants will diffuse back into the column through the fused-silica wall because their molecular sizes are too large. The volume of air that could be sucked into an evacuated column after opening for installation is equal to the column volume a few millilitres at most which is thousands of times less than the effective volume that could diffuse into open column ends during prolonged storage. I would also argue that using a septum to seal a column is a better choice than flame sealing. Flame sealing column ends destroys the stationary phase for several centimetres, activates the column inner surface where heated, and may force stationary-phase fragments and microscopic particles a significant distance into the column under the influence of the gas expanding from the heating. These fragments, once deposited in the stationary phase, would appear in subsequent chromatograms as bleed or contaminants if not removed during installation by trimming enough column length from both ends more than just the apparently heated and damaged portions at the very ends. I always like to trim at least one-half turn from each end of a column immediately before installing it. After sliding on the nut and ferrule and trimming a column to its final length, I like to clean the ends with a methanol-moistened wipe to remove any residual material.

A Seal Mass-flow controller Packing Liner

B D

Septum-purge controller

Split-vent filter E

Back-pressure regulator Column Figure 1: Simplified diagram of a typical back-pressure control system for a splitsplitless inlet. Letters AE refer to pressures measured at different points through the system, as explained in the text.

Pneumatic Side Effects Whether chromatographers use hydrogen, helium or nitrogen for their carrier gas, they must set pneumatic parameters to values that lie within their systems, inlets, and columns normal operating ranges. Choosing operating parameters that lie outside the capability of the pneumatic system to control them, the inlet to deliver them or the column to accept them can produce unusual and unanticipated side effects that chromatographers may misinterpret. The interaction between inlet pressure and split-flow settings can strongly influence system pneumatic behaviour. The type of column and pneumatic system determine the useful range of split flows and inlet pressures. Most pneumatic control systems deliver flowrates from approximately 1020 mL/min to as much as 5001000 mL/min at pressures ranging from 24 psig to 100150 psig (6801030 kPa). The full ranges of both pressure and flow settings, however, are not necessarily available simultaneously. Operating close to the maximum or minimum of either the pressure or the flow ranges at the same time may prevent a pneumatic system from reaching its pressure and flow set points, or the pneumatic system may appear to be operating correctly although neither the column flow-rate nor the split ratio actually is at the desired value, as indicated on the electronic pneumatic system readouts. Direct measurement of the column and split flow-rate will reveal the true situation. Lets take a look at how these circumstances can arise. Any fluid-flow system relies upon finite but ostensibly small pressure drops in its interconnecting tubing and through its operating parts to move gas and liquid from one point to another. In the instance of so-called back-pressure regulated GC pneumatic systems operating a splitsplitless inlet in the split mode, a mass-flow controller meters the carrier gas into the inlet system, and a back-pressure regulator presents a variable restriction to the splitvent flow from the inlet that produces the desired pressure drop. Figure 1 illustrates the principal components of a typical back-pressure pneumatic system for a splitsplitless inlet. In the split mode, a mass-flow controller delivers the total flow of carrier gas 100 mL/min, for example to the inlet system through a relatively long connecting tube. Inside the inlet itself, most of the flow passes through the inlet liner, and a small fraction roughly 35 mL/min sweeps under the septum area and exits through a septum-purge

GC connections

LCGC Europe - November 2001

flow controller. The remaining carrier flow then passes through any liner packing or other inlet liner geometries that may be present and past the column entrance. Here, a portion of carrier gas equal to the column mass flow enters the column. The remainder leaves the inlet and passes through a back-pressure regulator to vent. A split-vent filter, which I highly recommend, removes high-boiling-point material from the carrier-gas stream and protects the back-pressure regulator from sample contamination. As carrier gas moves through the system, its pressure drops slightly in the external tubing, pneumatic components and the inlet itself. In a back-pressure regulated system, the small pressure drop from point A to point B in Figure 1 is unimportant. The remaining pressure drops, from points B to C to D to E, however, can affect chromatography. Mechanical back-pressure systems monitor and control the set-point inlet pressure at point E, where a gauge or electronic readout is also usually attached. The actual column inlet pressure at point C, however, will be slightly higher than the indicated set point at point E. The difference between the pressures at C and E depends upon the individual system design and, more importantly, upon the carrier-gas flow-rate through that portion of the system. Higher flow-rates produce a greater pressure at point C, the column inlet, but the pressure at point E remains nearly constant. This situation means that the column inlet pressure, and thus peak retention times, will depend to a significant degree upon the split flow-rate, even though the indicated pressure at point E is constant. Retention times will be shorter at higher split flow-rates. One of electronic pneumatic systems strengths is their design flexibility. The electronic back-pressure controllers used in many systems permit a pressure sensor to be located at places other than point E. To overcome the above pressure-drop effect, most electronic pneumatic control systems place the back-pressure sensor at point D or point B. The pros and cons of either position are beyond the scope of this column. Each has its proponents, and both positions bring the pressure sensor as close as possible to the column entrance. In either instance, this arrangement results in a much more stable relationship between split flow and retention times. However, other situations can arise and defeat a mechanical or an electronic systems ability to control the carrier gas accurately.

High split flow with low inlet pressure:

Attempts to achieve high split flows at low column pressure drops will cause problems. For example, consider a 25 m 0.53 mm column operating at a 100:1 split ratio. At 50 C, this column needs only a 2.6 psig (17.8 kPa) pressure drop to achieve an average helium carrier-gas linear velocity of 30 cm/s. At this velocity, the column flowrate is 4.0 mL/min, and the desired 100:1 split ratio requires a split flow-rate of 400 mL/min. The pressure drop needed to push that much carrier gas through the inlet and the downstream pneumatic components from point B to point E in Figure 1 can generate a natural back pressure of 35 psig (2035 kPa) at point C, the column entrance, and this amount exceeds the desired set-point column pressure. It will produce a higher-thandesired linear velocity, shortened retention times and correspondingly lower split ratios. With manual pneumatic systems, operators may be unaware of this situation unless they measure the average linear gas velocity after setting the split flow-rate. An electronic pneumatic system will indicate a problem when the measured inlet pressure stabilizes at a higher level than the setpoint pressure. Substituting a shorter, narrower-bore column that requires a higher-pressure drop and a lower split flow-rate but still delivers approximately the same number of theoretical plates will solve this problem. Alternatively, using an on-column or direct inlet system with carrier-gas mass flow control may present an acceptable alternative if the sample concentration permits it. Low split flow with high column flow: A related situation arises when attempting to operate a wide-bore column at low split ratios and high column flow-rates. Imagine that a method specifies a 10 mL/min total split flow-rate through point A in Figure 1 for the same 25 m 0.53 mm column and a higher-than-optimum column flow of 60 cm/s linear velocity conditions that I have encountered more frequently than I would like. These parameters amount to an inlet set-point pressure of nearly 5 psig (35 kPa). At this low split flow-rate, excessive back pressure has no potential to raise the actual column inlet pressure higher than its set point. However, at 60 cm/s velocity the desired column flow-rate is 8.6 mL/min and only another 1.4 mL/min of carrier-gas flow is available to supply both the septum-purge and split-vent flows. This situation starves the system of carrier gas and causes the inlet pressure to fail to rise to its set point.

Instead, the column flow-rate will tend to settle close to the total split flow less the septum purge flow, which is at a lower column inlet pressure of roughly 34 psig (2230 kPa) for this example. The backpressure regulator shuts off completely, and an electronic pneumatic system will fail to enter a ready state. It may see this situation as the result of a significant carrier-gas leak, and it may enter a safetyshutdown mode after a few minutes. To avoid this problem, use a high-enough split flow-rate to ensure that sufficient carrier gas flows into the inlet system to supply the column, septum-purge and split-vent flows. If a trace-level sample requires a low split flow-rate in an attempt to attain a split ratio that is as small as possible, consider using splitless or oncolumn injection or raising the total split flow-rate sufficiently to deliver at least 20 mL/min to the inlet. Manual pneumatic users should be free of this kind of problem, because such systems usually measure the split-vent flow-rate at the exit of the back-pressure regulator, through point E in Figure 1. Setting the carrier-gas flow controller to deliver 10 mL/min at the split-vent exit in this configuration will result in sufficient flow through the system to supply the column, the septum purge and the split vent as desired, and it will raise the total split flow through point A to slightly more than 20 mL/min in this example. Conclusion Electronic pneumatic controls for GC splitsplitless inlets give chromatographers more flexibility and better control of the split flow and inlet pressure than do those of manual pneumatic systems. The convenience of simply pressing keys to set pneumatic systems may lead GC operators into failing to check the actual column flow or velocity and the split-vent flow-rate. It is easy to enter incorrect column dimensions, carrier-gas types and operating modes or conversely to fail to correct all the parameters when changing columns or methods. Even when all the parameters are correct, situations in which the pneumatic system is incapable of delivering the desired combination of flows and inlet pressure can arise. Analysts need to be aware of these limitations and be ready to switch to alternative injection modes or even to change to a different inlet when appropriate.

LCGC Europe - November 2001

GC connections

References
(1) J.V. Hinshaw, LCGC Eur., 14(7), 378383 (2001). (2) J.V. Hinshaw, LCGC Eur., 13(11), 812817 (2000). (3) J.E. Cahill and D.H. Tracy, J. High Resolut. Chromatogr., 21(10), 531539 (1998).

GC Connections editor John V. Hinshaw is president and principal scientist of ChromSource, Franklin, Tennessee, USA, and a member of the Editorial Advisory Board of LCGC Europe. Direct correspondence about this column to GC Connections, LCGC Europe, Advanstar House, Park West, Sealand Road, Chester CH1 4RN, UK, e-mail: dhills@advanstar.com For an ongoing discussion of GC issues with John Hinshaw and other chromatographers, visit the Chromatography Forum discussion group at http://www.chromforum.com

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