Sampling Valves

P IDs (piping and instrumentation diagrams) should identify instruments, sample locations, the presence of sample valves, nozzle blinding, and control points. Of particular importance are the bypasses and alternate feed locations. The isolation valves in these hues may leak and can distort the interpretation of the measurements. 

Understanding the positions of sample and other measurement locations within the equipment is also important. The presence or absence of isolation valves needs to be identified. While isolation valves may be too large for effective sampling, their absence will require that pipe fitters add them such that sample valves can be connected. This must be done in advance of any test. If analysts assume that samples are from a liquid stream when they are vapor or that temperature measurements are within a bed instead of outside it, interpretation of results could be corrupted. Analysts should also develop an understanding of control transmitters and stations. The connection between these two may be difficult to identify at this level in fully computer-controlled units. 

Unit checkout Check that required mechanical work has been completed, tags and blinds pulled, and temporary piping disconnected. Plant supervision must certify completion of work. Cancel all entry and work permits. Utility system has been commissioned. Check blind list and inspect lines close bleed, drain and sample valves. 

In practice, the retention volume of an unretained peak eluted at the dead volume (Vo), will be made up of the volume of mobile phase in the column (Vm) and extracolumn volumes, from sample valves, connecting tubes, unions, etc. (Ve)-... 

The introduction of the sample valve, however, helped establish radial equilibrium early in the separation but, unless some special sample spreading device is employed at the front of the column, equilibrium will not necessarily occur at the point of injection. The stream splitting process is depicted in Figure 2. 

There are two types of sample valve commonly used in LC, the internal loop valve and the external loop valve. In order to improve the seating and eliminate leaks, the valve faces are sometimes made from appropriate ceramics. The internal loop valves are largely used with small bore columns, that is to say columns having internal diameters of less than 1.5 mm. The external loop valves are used for larger diameter columns up to semi-preparative columns. 

The external loop valve is the more commonly used sampling system and offers a wider choice of readily adjustable sample sizes. A modified form of the external loop sample valve has become very popular for quantitative LC analysis, a diagram of which is shown in Figure 3. 

The basic difference between this type of valve and the normal external loop sample valve is the incorporation of an extra port at the front of the valve. This port allows the injection of a sample by a syringe directly into the front of the sample loop. Position (A) shows the load position. Injection in the front port causes the sample to flow into the sample loop. The tip of the needle passes through the rotor seal and, on... 

Figure 3. The Modified External Loop Sample Valve...

The peaks shown were obtained using a low dispersion UV detector (cell volume, 1.4 pi) in conjunction with a sample valve with a 1 pi internal loop. All tubes were of... 

Extra-column dispersion can arise in the sample valve, unions, frits, connecting tubing, and the sensor cell of the detector. The maximum sample volume, i.e., that volume that contributes less than 10% to the column variance, is determined by the type of column, dimensions of the column and the chromatographic characteristics of the solute. In practice, the majority of the permitted extra-column dispersion should... 

A low volume (0.2 pi) Valeo sample valve was employed with one end of the open tube connected directly to the valve and the other connected directly to the sensor cell of the detector. The UV detector was the LC 85B manufactured by Perkin Elmer, and specially designed to provide low dispersion with a sensor volume of about 1.4 pi. The total variance due to extra-column dispersion was maintained at... 

Unfortunately, some of the data that are required to calculate the specifications and operating conditions of the optimum column involve instrument specifications which are often not available from the instrument manufacturer. In particular, the total dispersion of the detector and its internal connecting tubes is rarely given. In a similar manner, a value for the dispersion that takes place in a sample valve is rarely provided by the manufactures. The valve, as discussed in a previous chapter, can make a significant contribution to the extra-column dispersion of the chromatographic system, which, as has also been shown, will determine the magnitude of the column radius. Sadly, it is often left to the analyst to experimentally determine these data. 

The solvent consumption appears to be in conflict with the corresponding optimum flow rates. Substances with high (a) values have a very high optimum flow rate (over 11 per min. for (a=1.2) and the column diameter is over 6 mm which would indicate a very large solvent consumption. However, because the separation is simple, a very rapid separation is achieved with analysis times of less than a second. As a consequence, only a few ml of solvent is necessary to complete the analysis. The apparatus, however, must be designed with an exceedingly fast response and very special sample valves would be necessary. In contrast, a very... 

Ideally, the sample should be taken from a valve installed specifically for sampling. When sampling valves are not installed the taking of samples from locations where sediment or water can collect, such as dead ends of piping, tank drains, and low points of large pipes and filter bowls, should be avoided if possible. If samples are taken from pipe drains, sufficient fluid should be drained before the sample is taken to ensure that the sample actually represents the system. Samples are not to be taken from the tops of... 

Sample injection system. Introduction of the sample is generally achieved in one of two ways, either by using syringe injection or through a sampling valve. 

Although the problems associated with septum injectors can be eliminated by using stop-flow septumless injection, currently the most widely used devices in commercial chromatographs are the microvolume sampling valves (Fig. 8.3) which enable samples to be introduced reproducibly into pressurised columns without significant interruption of the mobile phase flow. The sample is loaded at atmospheric pressure into an external loop in the valve and introduced into the mobile phase by an appropriate rotation of the valve. The volume of sample introduced, ranging from 2 piL to over 100 /iL, may be varied by changing... 

There are several types of sample introduction systems available for GC analysis. These include gas sampling valves, split and splitless injectors, on-column injection systems, programmed-temperature injectors, and concentrating devices. The sample introduction device used depends on the application. 

To a stainless steel reactor equipped with a heating mantle, a charging port, a condenser for removing ethylene glycol, an inert gas inlet, and a sampling valve were added 400 g of bis(2-hydroxyethyl)terephthalate, 136 g of ethylene glycol, and 0.035 g (or 0.225 g) of sodium acetate trihydrate. The temperature was raised to between 190 and 200°C in 1 h and then 454 g of waste polyester... 

The mass spectrometer sampling capillary or the dispersive infra-red analyzers used for continuous analysis and monitoring of the gas phase composition are situated between the reactor and the sampling valve, as close to the reactor as possible, in order to avoid any delay in the recording of changes in the composition of reactants or products. This delay should be taken into account when plotting simultaneously the time dependence of catalyst potential or current and gas phase concentration of the reactants or products. 

It must be pointed out that (Vm) refers to the volume of mobile phase in the column and not the total volume of mobile phase between the injection valve and the detector (Vo)- In practice, the dead volume (Vo) will include all the extra column volumes (Ve) involved in the sample valve, connecting tube detector cell etc. 

Each solvent passes from its reservoir directly to a pump and from the pump to a mixing manifold. After mixing, the solvents pass to the sample valve and column. The pumps control the actual program and are usually driven by stepping motors. The volume delivery of each solvent is controlled by the speed of the respective pump. In turn, the speed of each motor is precisely determined by the frequency of its power supply which can be either generated by external oscillators or, if the chromatograph is computer controlled, directly from the computer itself. 

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