Differential, detector operation

Microadsorption detectors (Table 3.5) have not been used to any large extent for column monitoring. These detectors operate by measuring the heat of adsorption of a solute as it passes over a temperature sensor. The thermistor may be located in the analytical column or in a smaller chamber containing an adsorbent and through which the effluent flows. These detectors are operated in a differential mode and changes as small as 0.001°C can be easily detected. The main reasons for the lack of use of such detectors... 

To differentiate tteir functions and modes of operation, the array collector of spatially dispersed m/z values is still called an array collector for historical reasons, but the other multipoint detector of a temporally dispersed range of m/z values is called a microchannel plate (typically used in time-of-flight instruments). 

Refractive index detectors. These bulk property detectors are based on the change of refractive index of the eluant from the column with respect to pure mobile phase. Although they are widely used, the refractive index detectors suffer from several disadvantages — lack of high sensitivity, lack of suitability for gradient elution, and the need for strict temperature control ( + 0.001 °C) to operate at their highest sensitivity. A pulseless pump, or a reciprocating pump equipped with a pulse dampener, must also be employed. The effect of these limitations may to some extent be overcome by the use of differential systems in which the column eluant is compared with a reference flow of pure mobile phase. The two chief types of RI detector are as follows. 

The basis of chromatography is in the differential migration of chemicals injected into a column. The carrier fluid takes the solutes through the bed used for elution (mobile phase). The bed is the stationary phase. Based on mobility, the retention-time detectors identify the fast and slow-moving molecules. Based on internal or external standards with defined concentration, all unknown molecules are calculated in a developed method by software. GC columns are installed in an oven which operates at a specified temperature. A diagram of an oven with GC column is shown in Figure 7.16. 

The second most widely used detector in HPLC is the differential refractometer (RI). Being a bulk property detector, the RI responds to all substances. As noted in Table 3 the detection limits are several orders of magnitude higher than obtained with the UV detector. Thus, one turns to the RI detector in those cases in which substances are non-UV active, e.g. lipids, prostaglandins. In addition, the RI detector finds use in preparative scale operation. Finally, relative to the UV detector, the RI is significantly more temperature and flow sensitive and cannot be used in gradient elution. 

The apparatus employed for this study was a Waters Associates Model ALC/GPC 300 with a differential refractometer as mass detector operated at room temperature. A 2 ml sample loop with polymer concentrations of 0.01-0.1 wt.% cUid a 5 ml siphon were employed with mobile phase flowrates in the reuige 1-8 ml/min. 

Chromatographic System. The isocratic liquid chromatograph used was a Waters Associates (Milford, MA) Model 24A alc which included a Model 6000A Solvent Delivery System, a Model 401 Differential Refractometer and a Model 440 Absorbance Detector operating at 254 nm and was fitted with a WISP automatic injector. The analog outputs of the UV absorbance detector or differential refractometer were recorded with a Model 730 Data Module (printer, plotter, integrator)(Waters). Eluent flow rate was 1.0 ml/min unless otherwise noted. 

The FALLS or MALLS detector measures r-related values a differential refractive index (DRI) detector is used to measure concentration, and the SEC supplies samples containing fractionated polymer solutions allowing both molecular weight and MWD to be determined. Further, polymer shape can be determined. This combination represents the most powerful one, based on ease of operation, variety of samples readily used, cost, means to determine polymer size, shape, and MWD available today. 

In operation, the viscometer of Figure 2 will generate two separate signal detector traces for recording. The differential log-anplifier will generate a viscosity (In hi) trace vdiile the concentration detector will generate a concentration (c) trace. 

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