Fluorine nonpolarity

If a molecule is diatomic, it is easy to decide whether it is polar or nonpolar. A diatomic molecule has only one kind of bond hence the polarity of the molecule is the same as the polarity of the bond. Hydrogen and fluorine (H2, F2) are nonpolar because the bonded atoms are identical and the bond is nonpolar. Hydrogen fluoride, HF, on the other hand, has a polar bond, so the molecule is polar. The bonding electrons spend more time near the fluorine atom so that there is a negative pole at that end and a positive pole at the hydrogen end. This is sometimes indicated by writing... 

Polymers with a sizable number of ionic groups and a relatively nonpolar backbone are known as ionomers. The term was first used for copolymers of ethylene with carboxylated monomers (such as methacrylic acid) present as salts, and cross-linked thermoreversibly by divalent metal ions. Such polymers are useful as transparent packaging and coating materials. Their fluorinated forms have been made into very interesting ion-exchange membranes (considered further below). 

The bond that holds two fluorine atoms together in an F2 molecule would be classified as nonpolar covalent because —... 

The axial orbitals used by phosphorus in this molecule can be considered as dp in character (see Chapter 4), which means they have no s character, whereas the orbitals in equatorial positions are sp2 hybrids. As expected, the fluorine atoms are found in axial positions and the molecule is nonpolar. This illustration shows the value of dipole moments in predicting the details of molecular structure. Table 6.1 shows dipole moments for a large number of inorganic molecules. 

Today it is claimed that the surface fluorination of polymers using F2 gas mixtures enhances a wide range of properties, e.g., low permeability to nonpolar liquids4 improved permselectivity,5-6 excellent wettability and adhesion,7 low friction coefficient (especially for elastomers),8 and chemical inertness.9 Obviously, these properties depend on the chemical composition ofthe fluorinated layer, which in turn is determined by the chemical structure ofthe base polymer, the composition of the F2 gas mixture, and the fluorination parameters. 

Apart from the benefits of excellent barrier properties with regard to the permeation of nonpolar liquids and good adhesion, little is known about the influence of surface fluorination on gas barrier properties. The permeability of only a few inorganic gases through surface-fluorinated plastics such as PE,19 PP, and PET20 have been evaluated to some extent. 

The molecular geometry of methane and of methyl fluoride is tetrahedral. In the case of methane, this symmetrical arrangement of polar covalent carbon-hydrogen bonds leads to a canceling of the bond polarities resulting in a nonpolar molecule. As a nonpolar molecule, the strongest intermolecular force in methane is a London force. In methyl fluoride, a fluorine atom replaces one of the hydrogen... 

The krypton atom in krypton difluoride does not obey the octet rule. The presence of five pair around the krypton leads to a trigonal bipyramidal electron-group geometry. The presence of three lone pairs and two bonding pairs around the krypton makes the molecule linear. The two krypton-fluorine bonds are polar covalent. However, in a linear molecule, the bond polarities pull directly against each other and cancel. Cancelled bond polarities make the molecule nonpolar. The strongest intermolecular force in the nonpolar krypton difluoride is London force. 

The fluorines are the most electronegative atoms present, and the bonds to them are polar covalent. The only nonpolar compound is the result of the polar C-F bonds pulling equally in opposite directions. 

Highly fluorinated molecules have a nonpolar character and an extremely low polarizability, inducing only weak intra- and intermolecular interactions. As a consequence, perfluorocarbons behave almost like ideal liquids they are very compressible and have very high vapor pressure. For example, the physical properties of perfluoro-hexane, heptafluorohexane, and hexane are reported in Table 1.2 The effect of the polar character of the hemifluorinated compound (heptafluorohexane) on the dielectric constant value is remarkable. 

Why doesn t it make sense to ask whether an element (like hydrogen or fluorine) engages in polar bonds versus nonpolar bonds ... 

Merritt et al. [124,170-174] carried out some of the earliest additions of fluorine to carbon-carbon double bonds. The fluorination of cis and trans propenyl benzene in a nonpolar solvent at low temperature gave predominantly erythro and threo difluorides respectively. More recently, Rozen [175] carried out similar reactions, but used a more polar solvent (trichlorofluoro methane, chloroform and ethanol) and a very low concentration of fluorine. Thus, in the fluorination of cis and trans 3-hexene- l-ol acetate (Fig. 72), syn addition occured to give exclusively the erythro and threo difluoro compounds respectively. Corresponding results were obtained in the addition of fluorine to other alkenes, including cyclic alkenes and cyclic enones. 

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