Dipole, induced

It is thus seen that the dipole-induced dipole propagation gives an exponential rather than an inverse x cube dependence of U x) with x. As with the dispersion potential, the interaction depends on the polarizability, but unlike the dispersion case, it is only the polarizability of the adsorbed species that is involved. The application of Eq. VI-43 to physical adsoiption is considered in Section XVII-7D. For the moment, the treatment illustrates how a long-range interaction can arise as a propagation of short-range interactions. 

The average cloud is spherically synnnetric with respect to the nucleus, but at any instant of time there may be a polarization of charge givmg rise to an instantaneous dipole moment. This instantaneous dipole induces a corresponding instantaneous dipole in the other atom and there is an interaction between the instantaneous dipoles. The dipole of either atom averages to zero over time, but the interaction energy does not because the instantaneous and induced dipoles are correlated and... 

Su T, Viggiano A A and Paulson J F 1992 The effect of the dipole-induced dipole potential on ion-polar molecule collision rate constants J. Chem. Phys. 96 5550-1... 

The raie gas atoms reveal through their deviation from ideal gas behavior that electrostatics alone cannot account for all non-bonded interactions, because all multipole moments are zero. Therefore, no dipole-dipole or dipole-induced dipole interactions are possible. Van der Waals first described the forces that give rise to such deviations from the expected behavior. This type of interaction between two atoms can be formulated by a Lennaid-Jones [12-6] function Eq. (27)). 

Alkanes and cycloalkanes are nonpolar and insoluble m water The forces of attraction between alkane molecules are induced dipole/induced dipole attractive forces The boiling points of alkanes increase as the number of carbon atoms increases Branched alkanes have lower boiling points than their unbranched isomers There is a limit to how closely two molecules can approach each other which is given by the sum of their van der Waals radii... 

Nonbonded interactions are the forces be tween atoms that aren t bonded to one another they may be either attractive or repulsive It often happens that the shape of a molecule may cause two atoms to be close in space even though they are sep arated from each other by many bonds Induced dipole/induced dipole interactions make van der Waals forces in alkanes weakly attractive at most distances but when two atoms are closer to each other than the sum of their van der Waals radii nuclear-nuclear and electron-electron repulsive forces between them dominate the fvan derwaais term The resulting destabilization is called van der Waals strain... 

Induced dipole/induced dipole forces are the only intermolecular attractive forces available to nonpolar molecules such as alkanes In addition to these forces polar molecules engage m dipole-dipole and dipole/mduced dipole attractions The dipole-dipole attractive force is easiest to visualize and is illustrated m Figure 4 3 Two molecules of a polar substance experience a mutual attraction between the positively polarized region of one molecule and the negatively polarized region of the other As its name implies the dipole/induced dipole force combines features of both the induced dipole/mduced dipole and dipole-dipole attractive forces A polar region of one mole cule alters the electron distribution m a nonpolar region of another m a direction that produces an attractive force between them... 

Dipole/induced dipole attraction (Section 4 6) A force of at traction that results when a species with a permanent dipole induces a complementary dipole in a second species... 

London force (Section 2 17) See induced dipole induced dipole attraction... 

Van der Waals forces (Section 2 17) Intermolecular forces that do not involve ions (dipole-dipole dipole/mduced dipole and induced dipole/induced dipole forces)... 

As argued above, this result is found to work best for substances in which both the 1,1 and 2,2 forces are either London or dipole-dipole. Even the case of one molecule with a permanent dipole moment interacting with a molecule which has only polarizability and no permanent dipole moment-such species interact by permanent dipole-induced dipole attraction-is not satisfactorily approximated by Eq. (8.46). In this context the like dissolves like rule means like with respect to the origin of intermolecular forces. 

Forces of Adsorption. Adsorption may be classified as chemisorption or physical adsorption, depending on the nature of the surface forces. In physical adsorption the forces are relatively weak, involving mainly van der Waals (induced dipole—induced dipole) interactions, supplemented in many cases by electrostatic contributions from field gradient—dipole or —quadmpole interactions. By contrast, in chemisorption there is significant electron transfer, equivalent to the formation of a chemical bond between the sorbate and the soHd surface. Such interactions are both stronger and more specific than the forces of physical adsorption and are obviously limited to monolayer coverage. The differences in the general features of physical and chemisorption systems (Table 1) can be understood on the basis of this difference in the nature of the surface forces. 

Attractive and Repulsive Forces. The force that causes small particles to stick together after colliding is van der Waals attraction. There are three van der Waals forces (/) Keesom-van der Waals, due to dipole—dipole interactions that have higher probabiUty of attractive orientations than nonattractive (2) Debye-van der Waals, due to dipole-induced dipole interactions (ie, uneven charge distribution is induced in a nonpolar material) and (J) London dispersion forces, which occur between two nonpolar substances. 

The induced counter-dipole can act in a similar manner to a permanent dipole and the electric forces between the two dipoles (permanent and induced) result in strong polar interactions. Typically, polarizable compounds are the aromatic hydrocarbons examples of their separation using induced dipole interactions to affect retention and selectivity will be given later. Dipole-induced dipole interaction is depicted in Figure 12. 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... 

Figure 12. Polar Interactions Dipole-Induced Dipole Interactions...

Alternatively, using a polyethylene glycol stationary phase, aromatic hydrocarbons can also be retained and separated primarily by dipole-induced dipole interactions combined with some dispersive interactions. Molecules can exhibit multiple interactive properties. For example, phenyl ethanol possesses both a dipole as a result of the hydroxyl group and is polarizable due to the aromatic ring. Complex molecules such as biopolymers can contain many different interactive groups. 

There are three types of interactions that contribute to van der Waals forces. These are interactions between freely rotating permanent dipoles (Keesom interactions), dipole-induced dipole interaction (Debye interactions), and instantaneous dip le-induced dipole (London dispersion interactions), with the total van der Waals force arising from the sum. The total van der Waals interaction between materials arise from the sum of all three of these contributions. 

These forces are electrical in nature, and in order to vaporize a substance, enough energy must be added to overcome them. Most alkanes have no measurable dipole moment, and therefore the only van der Waals force to be considered is the induced-dipole/induced-dipole attractive force. 

Extended assemblies of induced-dipole/induced-dipole attractions can accumulate to give substantial intennolecular- attractive forces. An alkane with a higher molecular-... 

Induced-dipole/induced-dipole attractions are ver-y weak forces individually, but a typical organic substance can par ticipate in so many of them that they are collectively the most impor tant of all the contributor s to intermolecular- attraction in the liquid state. They are the only forces of attraction possible between nonpolar- molecules such as alkanes. 

---