Newtonian Flow
Under Newtonian flow the viscosity of a fluid is defined as the tangential force per unit area that will provide unit relative velocity between two parallel plates in the fluid unit distance apart. When the shear force exceeds a value characteristic of the material plastic flow can occur but this rarely happens in chromatography. However, if the flow rapidly changes direction then turbulent flow is introduced which is characterized by an increase in solute diffusiity and Newtonian flow no longer exists. The introduction of turbulent flow into connecting tubes (tubes between column and detector) reduces peak dispersion and, thus, maintains column resolution.
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: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 Tubular-Conduits
Dispersion in Tubular Conduits
The dispersion
that takes place in open tubular conduits, as already described, results from
the parabolic velocity profile that occurs under conditions of Newtonian flow.
The distribution of fluid velocity across the tube under condition of Newtonian
flow, is depicted diagramatically in Figure 8A. Due to the relatively high
velocity at the center of the tube, and the very low velocity at the walls, the
center of the band of solute passing down the tube will move ahead of that
situated at the walls. This will result in band dispersion and this effect is
depicted in Figure 8B.
Figure
8. Dispersion Due to Newtonian Flow in
Connecting Tubes
EC-Dispersion Tubular-Conduits
Author: RPW Scott
Book:Liquid Chromatography Detectors
Section:HPLC-Detectors Dispersion Sensor-Volume Newtonian-Flow
smaller than the peak volume the effect will
merely give the peak an apparent dispersion. However, if the sensor volume
becomes of the same order of magnitude as the peak volume, then the peak
profile will be distorted and resolution will be lost. In the extreme
case two peaks could coexist in the sensor at one time and only a single peak
will be represented.
The
effect of viscous flow on dispersion will first be considered.
Dispersion in Detector Sensors Resulting from Newtonian Flow
Most sensor
volumes are cylindrical in shape, are relatively short in length, and have a
relatively small length-to-diameter ratio. The small length-to-diameter ratio
is in conflict with the premises assumed in the development of the Golay
equation for dispersion in an open tube. Atwood and Golay (11) extended the
theory of dispersion in open tubes to tubes having small length-to-diameter ratio.
The theory is complex and not relevant here as, if appropriate cell design is
HPLC-Detectors Dispersion Sensor-Volume Newtonian-Flow
Author: RPW Scott
Book:Extra Column Dispersion
Section:EC-Dispersion Sources Connecting-Tubes
Dispersion in Connecting Conduits
Dispersion
that occurs in connecting tubes, or conduits, is exclusively due to the
parabolic velocity profile of the mobile phase passing through it. This always
occurs when the mobile phase velocity is less
than the critical velocity (the velocity at the onset of turbulent flow). As the critical
velocity of gases and liquids is well above those used in practical gas and
liquid chromatography, this type of dispersion is always present unless the
parabolic flow pattern is disrupted. The conditions where a parabolic velocity
profile exists across a conduit is termed Newtonian Flow and any
connecting tube between the sample valve and the column, the column and the
detector, or any other cylindrical conduit will contribute to peak dispersion
EC-Dispersion Sources Connecting-Tubes
Author: RPW Scott
Book:Liquid Chromatography Detectors
Section:HPLC-Detectors Dispersion Connecting-Tubes
1. Dispersion from Connecting Tubes(Newtonian)
2. Dispersion from Sensor Cell Volume (Newtonian)
3. Dispersion from Sensor Cell Volume ( Dilution)
Each of these sources
of dispersion are controllable by careful sensor design and employing
appropriate cell geometry.
Dispersion in Connecting Tubes
The dispersion
that takes place in an open tube results from the parabolic velocity profile that
occurs under conditions of Newtonian flow, (i.e. when the velocity is
significantly below that which produces turbulence). Under condition of
Newtonian flow, the distribution of fluid velocity across the tube adopts a
parabolic profile as shown in figure 1. The velocity at the walls is virtually
zero and that at the center a maximum. This situation is depicted
diagramatically in Figure 1.
Figure 1.
The Parabolic Velocity Profile of a Solute Band Passing Through a Tube
Due to the
relatively
HPLC-Detectors Dispersion Connecting-Tubes