Split injection electronic pressure control

An alternative form of split injection is the timed split technique, Figure 6.11 [130,131,133]. In this case the column is connected directly to the valve and the valve actuator is controlled electronically to turn the valve to the inject position and back very rapidly with only a portion of the sample in the loop displaced to the column. Timed split allows variable volumes to be injected by changing the valve actuator tine and provides more reproducible splitting than the dynamic split technique. However, it suffers from many of the same problems as dynamic split, namely, poor accuracy, split ratios that depend on pressure, and high detection limits. 

Sample introduction is a major hardware problem for SFC. The sample solvent composition and the injection pressure and temperature can all affect sample introduction. The high solute diffusion and lower viscosity which favor supercritical fluids over liquid mobile phases can cause problems in injection. Back-diffusion can occur, causing broad solvent peaks and poor solute peak shape. There can also be a complex phase behavior as well as a solubility phenomenon taking place due to the fact that one may have combinations of supercritical fluid (neat or mixed with sample solvent), a subcritical liquified gas, sample solvents, and solute present simultaneously in the injector and column head [2]. All of these can contribute individually to reproducibility problems in SFC. Both dynamic and timed split modes are used for sample introduction in capillary SFC. Dynamic split injectors have a microvalve and splitter assembly. The amount of injection is based on the size of a fused silica restrictor. In the timed split mode, the SFC column is directly connected to the injection valve. Highspeed pneumatics and electronics are used along with a standard injection valve and actuator. Rapid actuation of the valve from the load to the inject position and back occurs in milliseconds. In this mode, one can program the time of injection on a computer and thus control the amount of injection. In packed-column SFC, an injector similar to HPLC is used and whole loop is injected on the column. The valve is switched either manually or automatically through a remote injector port. The injection is done under pressure. 

Figure 5.2.1. Simplified diagram of a Py-GC system (not to scale). The pyrolyser is schematized as a heated filament type. A piece of a deactivated fused silica line is passed through the injection port of the GC and goes directly into the pyrolyser. This piece of fused silica is connected to the column, which is put in the GC oven. The pneumatic system consists of (1) a mass flow controller, (2) an electronic flow sensor, (3) a solenoid valve, (4) a backpressure regulator, (5) a pressure gauge, and (6) septum purge controller. The connection (7) is closed when working in Py-GC mode, and connection (8) is open. (Connection (7) is open when the system works as a GC only.) Connection (9) is closed and connection (10) is open when the GC works in splitless mode (purge off). Connection (10) is closed and connection (9) is open when the GC works in split mode (purge on). No details on the GC oven or on the detector are given.

A schematic block diagram illustrating an entire DP-SCD detection system is shown in Fig. 2. An analytical system consists of a gas chromatogr h equipped with a split/splitless iigector with the option of a Pressurized Liquid Injection System (PLIS), wifli or without low diermal mass gas chromatogr q)hy apparatus, for sample introduction and sulfur speciation (if required) an electrically heated burner with an interface that controls the burner gas flows and temperature and a detector that contains a chemiluminescent reaction cell, ozone generator, optical filter, amplifier, and electronics. Lastly, a vacuum pump is used to keep file reaction cell under low pressure conditions to prevent loss of chemiluminescent species and to reduce collisional quenching. 

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