Carrier gases

Capillary column efficiency is dependent on the carrier gas used, the length and inner diameter of the column, the retention factor of the particular solute selected for calculation of the number of theoretical plates, and the film thickness of the 

The injector is a heated zone where the sample solution is introduced via a syringe to be then vaporized and mixed with the carrier gas which is the mobile phase. Except for rare applications, the carrier gas used in GC-MS is helium. If nitrogen and hydrogen are often used when a chromatograph is equipped with an FID, ECD, or NPD detector, these gases are rarely used with a mass spectrometer. They are not compatible with the use of an ion trap analyzer with internal ionization where the carrier gas also serves as cooling gas in the mass spectrometer (see Chapter 4). The inert carrier gas has no other function but to allow the elution of the compounds in the analytical column. 

Separation columns for partition chromatography are divided into two categories  

These consist of glass or steel tubes with an inside diameter (ID) of 1-50 mm. Columns with an ID greater than 5 mm are used for preparative GC. 

These consist of fused silica (silicon dioxide), alkali glass or borate glass. Their ID varies between 30 and 500 pm. Column lengths are usually between 1 and 100 m. 

In partition chromatography, a wide range of compounds are used as stationary liquid phases  

The stationary phases can differ in polarity. Examples of the most commonly used phases are  

---

Gas phase chromatography is a separation method in which the molecules are split between a stationary phase, a heavy solvent, and a mobile gas phase called the carrier gas. The separation takes place in a column containing the heavy solvent which can have the following forms ... 

The column is swept continuously by a carrier gas such as helium, hydrogen, nitrogen or argon. The sample is injected into the head of the column where it is vaporized and picked up by the carrier gas. In packed columns, the injected volume is on the order of a microliter, whereas in a capillary column a flow divider (split) is installed at the head of the column and only a tiny fraction of the volume injected, about one per cent, is carried into the column. The different components migrate through the length of the column by a continuous succession of equilibria between the stationary and mobile phases. The components are held up by their attraction for the stationary phase and their vaporization temperatures. 

This type of analysis requires several chromatographic columns and detectors. Hydrocarbons are measured with the aid of a flame ionization detector FID, while the other gases are analyzed using a katharometer. A large number of combinations of columns is possible considering the commutations between columns and, potentially, backflushing of the carrier gas. As an example, the hydrocarbons can be separated by a column packed with silicone or alumina while O2, N2 and CO will require a molecular sieve column. H2S is a special case because this gas is fixed irreversibly on a number of chromatographic supports. Its separation can be achieved on certain kinds of supports such as Porapak which are styrene-divinylbenzene copolymers. This type of phase is also used to analyze CO2 and water. 

The extent and manner of NDE applied in different shipyards has been the subject of a recently completed exercise within LR. The exercise involved randomly selected shipyards building ship types which included oil tankers, bulk carriers, gas carriers, container ships, ro-ro and general cargo ships. The variation in extent of applied NDE that was observed is summarised in Table 1. 

Figure Cl. 1.1. Schematic of a typical laser vaporization supersonic metal cluster source using a pulsed laser and a pulsed helium carrier gas.

Two different types of dynamic test have been devised to exploit this possibility. The first and more easily interpretable, used by Gibilaro et al [62] and by Dogu and Smith [63], employs a cell geometrically similar to the Wicke-Kallenbach apparatus, with a flow of carrier gas past each face of the porous septum. A sharp pulse of tracer is injected into the carrier stream on one side, and the response of the gas stream composition on the other side is then monitored as a function of time. Interpretation is based on the first two moments of the measured response curve, and Gibilaro et al refer explicitly to a model of the medium with a blmodal pore... 

The technique just described requires the porous medium to be sealed in a cell, so It cannot be used with pellets of irregular shape or granular material. For such materials an alternative technique Introduced by Eberly [64] is attractive. In Eberly s method the porous pellets or granules are packed into a tube through which the carrier gas flows steadily. A sharp pulse of tracer gas is then injected at the entry to the tube, and Its transit time through the tube and spreading at the exit are observed. A "chromatographic" system of this sort is very attractive to the experimenter,... 

Here z denotes distance measured along the tube from the injection point and f is the volume flow rate of carrier gas, per unit total cross-section. 

I he methyl iodide is transferred quantitatively (by means of a stream of a carrier gas such as carbon dioxide) to an absorption vessel where it either reacts with alcoholic silver nitrate solution and is finally estimated gravimetrically as Agl, or it is absorbed in an acetic acid solution containing bromine. In the latter case, iodine monobromide is first formed, further oxidation yielding iodic acid, which on subsequent treatment with acid KI solution liberates iodine which is finally estimated with thiosulphate (c/. p. 501). The advantage of this latter method is that six times the original quantity of iodine is finally liberated. 

Apparatus. The apparatus is made of Pyrex glass, in one piece. It consists of a shaped bulb A (Fig. 89 of about 30 ml. capacity in which the reaction takes place, provided with an inclined inlet B at the side and a vertical ascension tube D. B serves not only as an inlet for the admission of the carrier gas but also as the route by which the reagents and test sample are introduced into the apparatus. B ends in a small ground-glass joint into which fits ajoint carrying a capillary-tube which projects well down into the bulb A (the end of the capillary should be just above the liquid level when the apparatus is charged for the determination). The upper extension of this capillary beyond the joint is provided with a tap C to control the rate of flow of the carrier gas. 

Typically the effluent from a gas chromato graph is passed through a detector which feeds a sig nal to a recorder whenever a substance different from pure carrier gas leaves the column Thus one... 

In gas chromatography (GC) the sample, which may be a gas or liquid, is injected into a stream of an inert gaseous mobile phase (often called the carrier gas). The sample is carried through a packed or capillary column where the sample s components separate based on their ability to distribute themselves between the mobile and stationary phases. A schematic diagram of a typical gas chromatograph is shown in Figure 12.16. 

The most common mobile phases for GC are He, Ar, and N2, which have the advantage of being chemically inert toward both the sample and the stationary phase. The choice of which carrier gas to use is often determined by the instrument s detector. With packed columns the mobile-phase velocity is usually within the range of 25-150 mF/min, whereas flow rates for capillary columns are 1-25 mF/min. Actual flow rates are determined with a flow meter placed at the column outlet. 

In GC-MS effluent from the column is introduced directly into the mass spectrometer s ionization chamber in a manner that eliminates the majority of the carrier gas. In the ionization chamber all molecules (remaining carrier gas, solvent, and solutes) are ionized, and the ions are separated by their mass-to-charge ratio. Because each solute undergoes a characteristic fragmentation into smaller ions, its mass spectrum of ion intensity as a function of mass-to-charge ratio provides qualitative information that can be used to identify the solute. 

A variable-size simplex optimization of a gas chromatographic separation using oven temperature and carrier gas flow rate as factors is described in this experiment. 

The transfer efficiencies for ultrasonic nebulizers (USN) are about 20% at a sample uptake of about 1 ml/min. Almost 100% transfer efficiency can be attained at lower sample uptakes of about 5-20 pl/min. With ultrasonic nebulizers, carrier gas flows to the plasma flame can be lower than for pneumatic nebulizers because they transfer sample at a much higher rate. Furthermore, reduction in the carrier-gas flow means that the sample remains in the mass measurement system for a longer period of time which provides much better detection limits. 

The first form of aerosol modifier is a spray chamber. It is designed to produce turbulent flow in the argon carrier gas and to give time for the larger droplets to coalesce by collision. The result of coalescence, gravity, and turbulence is to deposit the larger droplets onto the walls of the spray chamber, from where the deposited liquid drains away. Since this liquid is all analyte solution, clearly some sample is wasted. Thus when sensitivity of analysis is an issue, it may be necessary to recycle this drained-off liquid back through the nebulizer. 

Having assisted desolvation in this way, the carrier gas then carries solvent vapor produced in the initial nebulization with more produced in the desolvation chamber. The relatively large amounts of solvent may be too much for the plasma flame, causing instability in its performance and, sometimes, putting out the flame completely. Therefore, the desolvation chamber usually contains a second section placed after the heating section. In this second part of the desolvation chamber, the carrier gas and entrained vapor are strongly cooled to temperatures of about 0 to -10 C. Much of the vapor condenses out onto the walls of the cooled section and is allowed to drain away. Since this drainage consists only of solvent and not analyte solution, it is normally directed to waste. 

Dynamic headspace GC/MS. The distillation of volatile and semivolatile compounds into a continuously flowing stream of carrier gas and into a device for trapping sample components. Contents of the trap are then introduced onto a gas chromatographic column. This is followed by mass spectrometric analysis of compounds eluting from the gas chromatograph. 

Effusion separator (or effusion enricher). An interface in which carrier gas is preferentially removed from the gas entering the mass spectrometer by effusive flow (e.g., through a porous tube or through a slit). This flow is usually molecular flow, such that the mean free path is much greater than the largest dimension of a traverse section of the channel. The flow characteristics are determined by collisions of the gas molecules with surfaces flow effects from molecular collisions are insignificant. 

---