Dipole-Dipole Polar interactions between molecules can result from either dipole-dipole interactions of dipole–induced dipole interactions. Dipole-dipole interactions arise from localized permanent dipoles. The two opposite charges are on the same molecules and, thus, neutralize each other so there is no net charge on the molecule as there is with an ion. However, the individual charges can interact with the individual charges of opposite sign on another molecule, and the interaction can be extremely strong. The energy of dipole-dipole interactions can approach the energy of a weak chemical bond. Due to the high energy of the dipole-dipole interactions, molecules can associate with each other (e.g., methanol-water association); this type of association is often called hydrogen bonding. The energy of interaction is directly proportional to the product of the polarizability of the molecule and the square of the dipole moment. The interaction energy is also inversely proportional to the sixth power of the distance between the interacting charges.

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Author: RPW Scott Book:The Mechanism of Chromatographic Retention
Section:Retention   Chromatographic-Interactions   Polar   Dipole-Induced-Dipole

), are termed polarizable. On close proximity of such compounds with a molecule having a permanent dipole, the electric field from the permanent dipole induces a counter dipole in the polarizable molecule.   Induced counter-dipole will behave in a similar manner to a permanent dipole and the electric forces between the two dipoles (permanent and induced) can result in strong polar interactions. Typical examples of polarizable compounds are the aromatic hydrocarbons. However, just as dipole-dipole interactions occur coincidentally with dispersive interactions, so are dipole-induced dipole interactions accompanied by dispersive interactions. It follows that using an n-alkane stationary phase, aromatic hydrocarbons can be retained and separated by purely dispersive interactions as in GC. This again is demonstrated in the upper chromatogram in figure 1. Alternatively, a polyethylene glycol stationary phase will separate aromatic hydrocarbons largely by dipole-induced dipole

Retention   Chromatographic-Interactions   Polar   Dipole-Induced-Dipole

Author: RPW Scott Book:Principles and Practice of Chromatography
Section:Principles   Distribution-Coefficient   Molecular   Dipole-Induced-Dipole

Principles   Distribution-Coefficient   Molecular   Dipole-Induced-Dipole

Author: RPW Scott Book:The Mechanism of Chromatographic Retention
Section:Retention   Chromatographic-Interactions   Polar   Dipole-Dipole

Dipole-Dipole Interactions. The strength of the intermolecular force involved in polar interaction is determined by the strength of the dipoles and can vary widely. In the extreme (e.g., the association of water with methanol) the dipole-dipole interaction energy can approach that of a chemical bond; such energies are involved in hydrogen bonding. To a first approximation, the energy (UP) that arises during the interaction between two dipolar molecules is given by,  

Retention   Chromatographic-Interactions   Polar   Dipole-Dipole

Author: RPW Scott Book:The Mechanism of Chromatographic Retention
Section:Retention   Chromatographic-Interactions   Polar

has also a significant number of different aromatic hydrocarbons present which, as already has been discussed (book 1), can be polarized and consequently interact with a polar stationary phase. Thus if a sample of gasoline is chromatographed on a strongly dispersive stationary phase the components would be separated roughly on a basis of molar volume. This is shown in the top chromatogram in figure 2. Polar Interactions Polar interactions can take two forms; those that result from direct dipole-dipole interaction (involving only molecules that have permanent dipoles) and those that result from dipole-induced dipoleinteraction Dipole-induced dipole interaction results from the interaction of a molecule with a permanent dipole and one that is polarizable. In general, dipole-dipole interactions are very strong polar interactions (e.g. the interaction of methanol with water) and dipole-induced dipole interactions relatively weak (e.g., the interaction of an ester with an aromatic

Retention   Chromatographic-Interactions   Polar

Author: RPW Scott Book:The Mechanism of Chromatographic Retention
Section:Retention   Chromatographic-Interactions   Polar   Dipole-Dipole

of dioxane. This reduces the field, as measured by external techniques, and gives a value for dioxane of only about one-third of that of a diethyl ether molecule alone. However, another molecule approaching one ether group of the dioxane molecule will be subject to the uncompensated field of a single dipole and interact accordingly. Consequently, although dioxane has a very low dipole moment of 0.45, it is still a very polar substance that is completely miscible with water. An impression of a dipole-dipole interaction is depicted in figure 3. The dipoles are shown interacting directly, but, it must be emphasized that behind the dipole-dipole interactions will be dispersive interactions from the random charge fluctuations that continuously take place on both molecules. In the example given above, the net molecular interaction will be a combination of both dispersive interactions from the fluctuating random charges and polar interactions from forces between the two dipoles. Examples of

Retention   Chromatographic-Interactions   Polar   Dipole-Dipole

Author: RPW Scott Book:Principles and Practice of Chromatography
Section:Principles   Distribution-Coefficient   Molecular   Dipole-Dipole

Principles   Distribution-Coefficient   Molecular   Dipole-Dipole


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