Concurrent solvent recondensation large sample volume splitless injection

Concurrent Solvent Recondensation Large Sample Volume (CRS‐LV) splitless injection overcomes the limitation of the maximum sample volume to 1–2 μL valid for classical splitless injection. It is based on control of the evaporation rate in the vaporizing chamber, utilization of a strong pressure increase in the injector resulting from solvent evaporation, and greatly accelerated transfer of the sample vapors from the injector into the inlet of an uncoated precolumn by recondensation of the solvent. The sample vapors are transferred into the column as rapidly as they are formed in the injector (concurrent transfer). 20–50 μL of liquid sample is injected with liquid band formation. The sample liquid is received by a small packing of deactivated glass wool positioned slightly above the column entrance at the bottom of the vaporizing chamber. Solvent evaporation strongly increases the pressure in the injector (auto pressure surge), provided the septum purge outlet is closed and the accessible volumes around the vaporizing chamber are small, driving the first vapors into the precolumn. Transfer continues to be fast because of recondensation of the solvent, obtained by keeping the oven temperature below the pressure‐corrected solvent boiling point. The uncoated precolumn must have sufficient capacity to retain most of the sample as a liquid. The experimental data show virtually complete absence of discrimination of volatile or high boiling components as well as high reproducibility.     

Large volume splitless injection with concurrent solvent recondensation: keeping the sample in place in the hot vaporizing chamber

An injector liner packed with a plug of glass wool is compared with a laminar and a mini laminar liner for large volume (20-50 microL) splitless injection with concurrent solvent recondensation (CSR-LV splitless injection). Videos from experiments with perylene solutions injected into imitation injectors show that glass wool perfectly arrested the sample liquid and kept it in place until the solvent had evaporated. The sample must be transferred from the needle to the glass wool as a band, avoiding 'thermospraying' by partial solvent evaporation inside the needle. The liquid contacted the liner wall when the band was directed towards it, but from there it was largely diverted to the glass wool. In the laminar liners, part of the liquid remained and evaporated at the entrance of the obstacle, while the other proceeded to the center cavity. Vapors formed in the center cavity drove liquid from the entrance of the obstacle upwards, but the importance of such problems could not be verified in the real injector. Some liquid split into small droplets broke through the obstacle and entered the column. Breakthrough through the laminar liners was confirmed by a chromatographic experiment. An improved design of a laminar liner for large volume injection is discussed as a promising alternative if glass wool causes problems originating from insufficient inertness.     

Injector chambers for classical GC splitless injection must be large!

Injector overflow is determined quantitatively by analysis of the septum purge effluent. Vaporizing chambers must have an internal volume of about 1 ml (e.g. 80 × 3.6 mm i.d.). This allows splitless injection of volumes between 1 and 2.5 μl, depending on the solvent. The septum purge should be closed during splitless transfer to prevent losses by back-diffusion.     

Large volume sample application by a simplified “closed” on-column injector in capillary gas chromatography

Summary A new simplified version of a closed on-column injector is introduced. Because of its design isobaric injection conditions do not have to be followed and a wide range of injection temperatures above the boiling point of the sample solvent can be chosen for on-column injections in capillary gas chromatography. Also, when following certain basic injection rules, injections of large sample volumes (20 l or more) give accurate and reproducible results without further problems.Presented at the 17th International Symposium on Chromatography, September 25–30, 1988, Vienna, Austria.     

PTV splitless injection of sample volumes up to 20 μl

PTV splitless injection cannot compete with on-column injection as far as simplicity, reliability, and accuracy of quantitative analysis is concerned. However, PTV splitless injection is attractive for trace analysis of samples containing high concentrations of involatile sample by-products. Maximum injection volumes are limited by the amount of liquid that can be retained within the PTV injector chamber and are around 20–30 μl injected at once. Solvent evaporation must be carried out in such a way that injector overflow is avoided.     

A new configuration for coupling purge-and-trap/cryogenic focusing/capillary column gas chromatography with splitless injection mode

A new configuration for coupling a purge-and-trap unit to a capillary column gas chromatograph via a cryogenic focusing interface has been developed. In this configuration, the precolumn of the cryogenic focusing interface was inserted through the septum of a split/splitless injection port where it served as both sample transfer and carrier gas supply lines. The injection port of the gas chromatograph was modified by plugging the carrier gas and the septum purge lines. This configuration allowed for the desorption of analytes at high flow rates while maintaining low, analytical-column flow rates which are necessary for optimum capillary column operation. The capillary column flow rate is still controlled by the column backpressure regulator. Chromatograms of purgeable aromatics exhibited improved resolution, especially for early eluting components compared to those obtained by direct liquid injection using the normal splitless injection mode. Quantitative sample transfer to the analytical column afforded excellent linearity and reproducibility of compounds studied.     

Improving splitless injection with electronic pressure programming

An experimental injection port has been designed for split or splitless sample introduction in capillary gas chromatography; the inlet uses electronic pressure control, in order that the column head pressure may be set from the GC keyboard, and the inlet may be used in the constant flow or constant pressure modes. Alternatively, the column head pressure may be programmed up or down during a GC run in a manner analogous to even temperature programming. Using electronic pressure control, a method was developed which used high column head pressures (high column flow rates) at the time of injection, followed by rapid reduction of the pressure to that required for optimum GC separation. In this way, high flow rates could be used at the time of splitless injection to reduce sample discrimination, while lower flow rates could be used for the separation. Using this method, up to 5 μl of a test sample could be injected in the splitless mode with no discrimination; in another experiment, 2.3 times as much sample was introduced into the column by using electronic pressure programming. Some GC peak broadening was observed in the first experiment.     

Large volume injection for preparative supercritical fluid chromatography

Summary A large volume injection system for preparative supercritical fluid chromatography is described. The method which is based on the solvent venting technique coupled with dilution of the sample solution consists of three steps. The first step is continuous dilution of the sample solution with liquid carbon dioxide at a controlled flow rate. The second step is solvent removal and solute trapping in a packed trap column. Combination of these two steps results in efficient solvent removal and the volume of sample which can be injected in a single injection becomes virtually unlimited. The third step is transfer and re-concentration of the solutes from the trap column on to the separation column with the pressures of both columns controlled independently; the final step is the separation. With this method, mass overloading behavior has been investigated and preparative separations performed.     

Determination of biogenic quaternary ammonium compounds on fused silica capillary columns with a splitless injector as a chemical reactor/pyrolysis chamber

A conventional splitless injector is used as a pyrolysis chamber or chemical reactor for the N-demethylation of acetylcholine and other choline esters. The novel uses of 2-aminoethanol as a N-demethylation reagent in splitless injection and bonded-phase fused silica capillary columns in the separation of the tertiary amine derivatives of choline esters are described. A comparison is made between non-polar and moderately polar fused silica capillary columns in the separation of choline esters.     

Modification of a packed GC injector to a versatile capillary injector

A modification of a packed GC injector to a capillary injector is presented using a simple device which is connected to the GC column by an adsorption-free connector. It permits injections of large sample volumes up to 500 μl hexane solutions on normal 0.3 mm i.d. capillary columns. No special requirements for the stationary phase are necessary. Involatile residues remain inside the device which can be exchanged easily. High performance of separation and quantification is achieved.     

The effects of inlet liner configuration and septum purge flow rate on discrimination in splitless injection

An unmodified split/splitless inlet system using forward-pressure controlled pneumatics was operated in splitless injection mode with several inlet liners under a range of septum purge flow rates. The relative recovery (discrimination) of hydrocarbons ranging from n-C₈ to n-C₂₀ depended strongly upon the injected sample volume with open-ended liners at high septum purge flow rates of e.g. 50 mL/min. Little or no discrimination was observed at septum purge flows of 2–3 mL/min. The same inlet was also operated in a back-pressure regulated configuration that produced mass discrimination similar to that observed with the higher septum purge flows in the forward-pressure configuration. An inlet liner with a restricted inlet and outlet gave mass-discrimination levels independent of septum purge flow rate, but in the reverse sense of that observed with open-ended liners. Preferential volatile-component losses out of the inlet liner to the septum purge vent are principally responsible for the observed mass discrimination with openended liners, while mass-dependent losses with doubly-restricted liners seem due to slow sample evaporation.     

Large volume sample introduction using temperature programmable injectors: Implications of liner diameter

Temperature programmable injectors with liner diameters ranging from 1 to 3.5 mm are evaluated and compared for solvent split injection of large volumes in capillary gas chromatography. The liner dimensions determine whether a large sample volume can be introduced rapidly or has to be introduced in a speed controlled manner. The effect of the injection technique used on the recovery of n-alkanes is evaluated. Furthermore the influence of the liner diameter on the occurrence of thermal degradation during splitless transfer to the analytical column is studied. Guidelines are given for the selection of the PTV liner internal diameter best suited for specific applications.     

Dual-purpose gas chromatographic injection device for pressurized liquid and gas injection

A dual-purpose gas chromatographic injection device, capable of injecting pressurized liquid sample of up to 5000 psig and gas sample with a volume as high as 5000 μL, has been successfully developed and implemented. The injection device is synergized by the effectiveness of a classical flash vaporization of a syringe injection and the reliability of a proven rotary valve. Depending on the matrix involved, this injection device employs either a commercially available four-port internal valve for liquid sampling or a six-port external valve for gas sampling, a modified removable needle used in standard liquid syringe, and an auxiliary flow stream that can be either mechanical or electronic flow controlled for solute transfer. For pressurized liquid, the device was found suitable of up to nC₁₆ hydrocarbon with no observable carry-over despite the injection device was operating at ambient temperature. A relative standard deviation of less than 2% (n = 20) was obtained for hydrocarbon compounds ranging from nC₈ to nC₁₆. For gas injection, the device performed well even under difficult chromatographic conditions such as with a low column inlet pressure of less than 1 psig. A relative standard deviation of less than 0.5% (n = 10) was obtained for reactive sulfur compounds such as alkyl mercaptans. The device can be operated manually or automated with pneumatic or electrical actuator, is platform neutral, and can be moved amongst instruments without hardware modification as well as implemented for on-line or in situ applications. In this paper, the utility of the device was also demonstrated with selected GC applications of industrial significance.     

Simple Analysis of Amphetamines in Human Whole Blood and Urine by Headspace Capillary Gas Chromatography with Large Volume Injection

Summary A very simple method for the analysis of methamphetamine and amphetamine in human whole blood and urine by headspace gas chromatography (GC) has been presented. It neither needs solid-phase microextraction nor cryogenic trapping devices, but only a conventional capillary GC instrument with flame ionization detection (FID). The two special points to be mentioned in this method are the in-matrix derivatization of amphetamines for vaporization and the capability of injection of as large as 5 mL of the headspace vapor into a GC instrument in the splitless mode for sensitive detection. After heating a whole blood or urine sample containing amphetamines, -methylbenzylamine (internal standard, IS) and heptafluoro-n-butyryl chloride under alkaline conditions in a 7.0-mL vial at 90 °C for 20 min, 5 mL of the headspace vapor was drawn with a glass syringe and injected into the gas chromatograph. During injection the column was at 40 °C to trap the analytes, and then the oven temperature was programmed up to 320 °C. Sharp peaks were obtained for each analyte and IS, and only a relatively small number of background impurity peaks for the whole blood and urine samples. The detection limits for each amphetamine were estimated to be 0.1 g mL^–1 for whole blood and 0.03 g mL^–1 for urine. Precision and linearity were also tested to confirm the reliability. Methamphetamine and amphetamine could be determined from whole blood and urine obtained at autopsy in three methamphetamine poisoning cases. The identity of each peak appearing in the gas chromatograms was confirmed by GC/mass spectrometry.