Polar Phase
A polar phase is one that has strong polar interactivity and, thus, will interact strongly with other polar substances. Polar phases have hydroxyl groups, amino groups, ester groups, ketone groups etc. that have strong permanent dipoles. Weak polar phases would have ether groups, or aromatic nuclei, the latter being polarizable but with no permanent dipole. Typical polar mobile phases would be water, methanol, acetonitrile, ethanol, etc and typical polar stationary phases would be silica gel, polyethyleneglycol, dinonyl phthalate, cyano bonded phase etc.
Author: RPW Scott
Book:Liquid Chromatography
Section:HPLC HPLC-Mobile-Phases
stationary phase must also be dispersive (a reversed phase) to promote
dispersive interaction with the solutes and provide adequate retention and
selectivity. If the solutes are strongly polar then a polarizable stationary
phase (one containing aromatic rings or cyano groups) would be appropriate to
separate the solutes by polar and induced polar interactions. If the solutes
are weakly polar then a strong polar stationary phase would be required (such
as silica gel) to separate the solute by polar interactions.
The mobile
phase must be chosen to complement the stationary phase so that the selected
interactions are concentrated in the stationary phase. Thus, a reversed phase
having strong dispersive interactions would be used with a strongly polar
mobile phase (e.g., mixtures of methanol and water acetonitrile and
water or tetrahydrofuran and water). In contrast, if the strongly polar silica
gel is selected for the stationary phase then a strongly dispersive mobile
phase would be
HPLC HPLC-Mobile-Phases
Author: RPW Scott
Book:The Mechanism of Chromatographic Retention
Section:Retention Chromatographic-Interactions Polar
be predominantly dispersive and in LC the eluting mobile phase
would be predominantly polar (cf. reverse phase chromatography). If the
stationary phase is largely polar in character then the retention mechanism
will be predominantly polar and in LC the eluting mobile phase would-be made
dispersive (cf. normal phase chromatography).
An example of
dispersive and polar interactions is afforded by the separation of the gasoline
sample on both a highly dispersive stationary phase, and a strongly polar
stationary phase. The separations are shown in figure 2. GC gives a clear
indication of the retentive character of the stationary phase as there are no
significant interactions in the mobile phase. Gasoline has a relatively high
proportion of aliphatic hydrocarbons which can only interact dispersively with
any stationary phase. However, it has also a significant number of different
aromatic hydrocarbons present which, as already has been discussed (book 1),
can be polarized and
Retention Chromatographic-Interactions Polar
Author: RPW Scott
Book:The Mechanism of Chromatographic Retention
Section:Retention Chiral-Chromatography Chiral-Polysiloxane-Stationary-Phases
shown in figure 36.
Two conditions are employed, the first used pure ethanol as the mobile phase,
which is relatively dispersive, and in the second, a mobile phase that contains
90% of water which will be strongly polar. With pure ethanol there will be
relatively strong dispersive interactions in the mobile phase which, in any
event, will significantly exceed any dispersive interactions involved between
the solute and the stationary phase. It follows that the dominant retentive
forces will be polar or ionic in nature. In the second case, the mobile
phase is predominantly water and thus provides very strong polar interactions
with the solute but very weak dispersive interactions. It also follows, that
the retention forces of the stationary phase, in this case, will be dominantly
dispersive in nature.
The two
separations demonstrates a very useful flexibility of Vancomycin as a
stationary phase. Adjusting the mobile phase composition, can be very effective
for separating solutes
Retention Chiral-Chromatography Chiral-Polysiloxane-Stationary-Phases
Author: RPW Scott
Book:The Mechanism of Chromatographic Retention
Section:Retention Chromatographic-Interactions Polar Dipole-Dipole
that
contain permanent dipoles and can exhibit polar interactions with other
molecules are alcohols, esters, ethers, amines, amides, nitriles, etc.
The retentive
characteristics of a polar stationary phase are displayed in the lower
chromatogram in figure 2 and can be compared with the retentive characteristics
of a dispersive phase shown in the chromatogram above. The polar stationary
phase is a cyanopropyl polymer that exhibits relatively weak dispersive
interactions but strong polar interactions. The aliphatic hydrocarbons, that
are well retained by the dispersive stationary phase, are rapidly eluted on the
polar phase but the aromatics are strongly retained and well resolved from one
another. On the dispersive stationary phase, all the solutes are spread along
the chromatogram, roughly in order of their increasing molecular weights.
Finally, it
has been shown that the polarizability of a substance containing no
dipoles will, among other factors, determine the
Retention Chromatographic-Interactions Polar Dipole-Dipole
Author: RPW Scott
Book:Preparative Chromatography
Section:Preparative Criteria-for-Successful-Operation
interest will remain in the stationary phase. As a simple example,
if the solute of interest is strongly polar, and the neighboring substance
dispersive, then the stationary phase must be polar (e.g., silica gel in
LC, or perhaps, polyethylene glycol in
GC) and in LC the mobile phase would be made predominantly dispersive (e.g.,
n-heptane or methylene dichloride or mixtures of both) so that polar
selectivity remains dominant in the stationary phase. Unfortunately, all
substances are not simply polar or dispersive or ionic but can exhibit various
combinations of all three interactive characteristics. It follows, that the
stationary phase will also need to have the appropriate mixture of interactive
properties to maximize selectivity and in contrast the interactive character of
the mobile phase will need to oppositely balanced to ensure maximum selectivity
still resides in the stationary phase. Under some circumstances the selectivity
of the mobile phase can also be exploited to
Preparative Criteria-for-Successful-Operation
Author: RPW Scott
Book:Capillary Chromatography
Section:Capillary Applications Gasoline
ūC would indicates that the dispersive contributions by the stationary phase to solute retention were relatively minor. In contrast, the C8 ethylhexanoic acids are eluted just before the n-pentadecane exposing the very strong polar character of the phase. The isomeric dichlorobenzenes demonstrate a good selectivity for the spatial isomers and there is also an effective separation of the two enantiomers. The separation of the dichloro-benzenes again indicates that the presence of strong induced polar interactions between the aromatic nuclei of the solutes and the strong polar groups of the stationary phase. Similarly, the strong polar interactions that are seen to occur between the carboxyl group of the enantiomer that penetrates closest to the stationary phase, and the neighboring polar groups of the interactive site obviously provide the necessary selectivity to resolve it from the other, slightly more excluded, enantiomer.
The Analysis of Gasoline
Gasoline is a multi-
Capillary Applications Gasoline