Flow-Cell
Flow cell is the term usually given to the sensor volume of a chromatography detector (it may also be given to the detector sensor volume used for other techniques but its use is mostly restricted to chromatography). In LC, the cell volume must be small (preferably less than 8 l) so that it can only contain a fraction of the volume of the smallest eluted peak (ca 0.3 x peak volume). To reduce peak dispersion (peak spreading), the cell length must be much greater than the cell diameter. Typically the cell would be about 10 mm long and about 0.8 mm ID giving a cell volume of about 5l. In cells used for light absorption, the connections to the cell must be at either end and constructed so as to direct the stream of mobile phase from the column onto the face of the window. This arrangement requires the flow to reverse and produce strong mixing and, thus, minimize peak dispersion. The arrangement of the exit tube should be the same so that the stream of mobile phase axial to the cell must turn and exit through the tube oriented in the opposite direction, again facilitating mixing and reduction of peak dispersion. For GC detectors (e.g. the thermal conductivity detector), and for a packed column, the sensor cell can be much larger than in LC as the mobile phase flow rate is also much larger and the peak volume also much greater. Volumes of 0.5 to 1 ml can often be tolerated, but this is not so for GC capillary columns. In most capillary GC instruments the FID is used as the detector which is not concentration sensitive but mass sensitive and, thus, the volume of the sensor is not important. If, however, a concentration sensitive detector is used with a capillary column then, as the peak volumes can be only a fraction of a micro-liter, the restrictions on flow cell volume are extremely severe. Detectors that require flow cells should be avoided, if possible, when using capillary columns.
Author: RPW Scott
Book:Extra Column Dispersion
Section:EC-Dispersion Newtonian-Flow
in
the cell (i.e. the length of the cell) the peak can exhibit various
degrees of dispersion and types of distortion. However, it must be emphasized
that the curves shown in figure 18 only occur when there is true Newtonian flow
through the cell (i.e., all flow rates are below the maximum where
turbulent flow is initiated). If, by appropriate design, the parabolic velocity
profile of the fluid flowing through the cell can be disrupted, then the
dispersion and distortion arising from Newtonian Flow can be virtually
eliminated.
In practice,
the disruption of the normal parabolic velocity profile of the fluid flowing
through the cell can be readily achieved by modifying the manner in which the
conduits cause the mobile phase to enter and exit the cell. The conduit
connections to the cell are oriented to
produce secondary flow in the manner shown in figure 19. Mobile phase enters
the cell at an angle so that fluid stream is directed at the cell window. As a
result of this, the
EC-Dispersion Newtonian-Flow
Author: RPW Scott
Book:Gas Chromatography - Tandem Techniques
Section:GC-Tandem GC-Spectroscopic-Systems UV-Visible-Absorption-Measurement Multi-Wavelength-Dispersive-Spectrometer
having a given extinction coefficient (k), (l) should be increased. However, in a flow-through sensor cell of a GC/spectrometer combination, the extent to which the path length can be increased is limited, as the total volume of the sensor cell must be restricted to ensure minimum peak dispersion and only a small fraction of a peak can be allowed to exist in the cell at any one time (4). To restrict peak dispersion and maintain a small sensor volume, it follows that the radius of the sensor cell must also be reduced as (l) is increased. This results in less light falling on the photoÐcell which, in turn, will reduce the signalÐtoÐnoise ratio and, thus, the sensor sensitivity, or minimum detectable concentration. Consequently, increasing the sensor sensitivity by increasing the path length has limitations and a wellÐdesigned cell involves a careful compromise between cell radius and length to provide the maximum sensitivity. Most modern UV spectrometer sensor's have path lengths
GC-Tandem GC-Spectroscopic-Systems UV-Visible-Absorption-Measurement Multi-Wavelength-Dispersive-Spectrometer
Author: RPW Scott
Book:Liquid Chromatography Detectors
Section:HPLC-Detectors Dispersion Sensor-Volume Newtonian-Flow
nbsp;
Figure 6 The Design of a
Modern Absorption Cell
The Newtonian
flow is distorted by the manner in which the inlet and outlet conduits are
connected to and from the cell. Mobile phase enters the cell at an angle that
is directed at the cell window. It follows, that the mobile phase flow has to
virtually reverse its direction to pass through the cell producing a swirling
action which introduces strong radial flow and disrupts the Newtonian flow. The
effect also occurs at the exit end of the cell. The flow along the axis of the
cell now must reverse its direction to pass out of the port which is
accomplished by attaching the exit conduit at an angle to the axis of the cell.
Employing this type of entry and exit connections eliminates dispersion
resulting from viscous flow
HPLC-Detectors Dispersion Sensor-Volume Newtonian-Flow
Author: RPW Scott
Book:Extra Column Dispersion
Section:EC-Dispersion Sensor-Volume Viscous-Flow
used to produced the elution curves in the lower chromatogram was 1 m
long, 1 mm I.D. and the same solvent was used at a flow rate of 40 ml/min Benzene was also used a the solute. It
is seen that the reduction in cell volume has a dramatic effect on both
peak width and peak shape. The large 25 ml
cell causes significant peak asymmetry as well as excessive peak dispersion A
result which is predicted by the work of Atwood and Golay (11) which is
discussed below. It is seen that the large sensor cell has a disastrous effect
on the band width of the solute eluted from the microbore column. Clearly, even
cell volumes of 3 ml are too large for
use with 1 mm I.D. columns and relatively few contemporary detectors have cell
volumes less than 3 ml.
J.
Chromatogr. 169(1979)51
Figure 17.
Peak Profiles from Detector Having Different Cell Volumes
EC-Dispersion Sensor-Volume Viscous-Flow
Author: RPW Scott
Book:Liquid Chromatography Detectors
Section:HPLC-Detectors Dispersion Sensor-Volume Newtonian-Flow
Dispersion in the Detector Sensor Volume
The finite
nature of the detector sensor volume can cause peak dispersion and contribute
to the peak variance by two processes. Firstly there will be dispersion
resulting from the Newtonian flow of fluid through the cell in much the same
manner as the flow of a viscous fluid through an open tube. This will furnish a
variance similar in form to that predicted by Golay but, as the tube length is
small and the tube length to radius ratio much larger than that from a
connecting tube, a different equation is necessary to describe the dispersion
effect.
Secondly,
there will be a peak spreading which results from the finite volume of the
sensor. If the sensor has a significant volume, the concentration
HPLC-Detectors Dispersion Sensor-Volume Newtonian-Flow
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Flow-Sensitivity
i.e.
Thus, a knowledge of (NP)
can be used in detector design when a particular sensitivity is the objective.
Flow Sensitivity
Flow sensitivity is another detector property
that can have a significant effect on long term noise and, consequently, also
on the detector MDC. Again it is the bulk property detectors that are the most
likely exhibit high flow sensitivities (e.g.,
the katharometer). To reduce its flow sensitivity, the katharometer is usually
fitted with a reference cell through which a flow of mobile phase also passes.
The two sensors for the column flow and the reference flow are placed in the
arms of a Wheatstone bridge so that any changes in flow rate are to a large
extent compensated. The flow sensitivity (DQ) is defined in a
similar manner to pressure sensitivity (i.e.
mV/ml/min). The flow sensitivity can be used to calculate the flow change (NQ)
that would provide a signal
GC-Detectors Flow-Sensitivity