Forces, intermolecular London

The term polymer is derived from the Greek words poly and meros, meaning many parts. We noted in the last section that the existence of these parts was acknowledged before the nature of the interaction which held them together was known. Today we realize that ordinary covalent bonds are the intramolecular forces which keep the polymer molecule intact. In addition, the usual type of intermolecular forces—hydrogen bonds, dipole-dipole interactions, and London forces—hold assemblies of these molecules together in the bulk state. The only thing that is remarkable about these molecules is their size, but that feature is remarkable indeed. 

Polyethylene. The crystal structure of this polymer is essentially the same as those of linear alkanes containing 20-40 carbon atoms, and the values of Tjj and AHf j are what would be expected on the basis of an extrapolation from data on the alkanes. Since there are no chain substituents or intermolecular forces other than London forces in polyethylene, we shall compare other polymers to it as a reference substance. 

As the bulkiness of the substituents increases, the chains are prevented from coming into intimate contact in the crystal. The intermolecular forces which hold these crystals together are all London forces, and these become weaker as the crystals loosen up owing to substituent bulkiness. Accordingly, the value for the heat of fusion decreases moving down Table 4.2. 

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. 

In Chapter 6, the polarizability of molecules was considered as one factor related to both London and dipole-induced dipole intermolecular forces. The data shown in Table 9.6 confirm many of the observations that can be made about physical properties. For example, in the case of F2, Cl2, and Br2, the London forces that arise from the increase in polarizability result in a general increase in boiling point. 

In dimethyl ether, the oxygen atom is sp3 hybridized. In creating two single bonds, each bond is formed by the overlap of one of its sp3 hybrid orbitals with the sp3 hybrid orbital on the adjacent carbon atom. Each of the remaining two hybrid orbitals on the oxygen atom contain a lone pair of electrons. The resulting molecule is polar. The intermolecular forces found operating between molecules of dimethyl ether are therefore dipole-dipole interactions and London forces. 

The weakest of all the intermolecular forces in nature are always London dispersion forces. 

Each of the eight substances will exhibit London forces since they are present in everything containing electrons. London forces are only the strongest type of intermolecular force if there are no other attractions present. The most convenient method of analyzing this problem is to leave consideration of London forces to the last. 

We can begin with any of the intermolecular forces other than London forces. It is usually easiest to begin with the normal bonds (covalent, ionic, and metallic). Bonds only occur in specific circumstances. For example, metallic bonds only occur in metals or metal alloys. The only metal or alloy in the seven substance fist is iron. For this reason, the strongest intermolecular force in iron is metallic bonding. 

We now have three substances remaining methane, CH4, methyl fluoride, CH3F, and krypton difluoride, KrF2. We also have two types of intermolecular force remaining dipole-dipole forces and London forces. In order to match these substances and forces we must know which of the substances are polar and which are nonpolar. Polar substances utilize dipole-dipole forces, while nonpolar substances utilize London forces. To determine the polarity of each substance, we must draw a Lewis structure for the substance (Chapter 9) and use valence-shell electron pair repulsion (VSEPR) (Chapter 10). The Lewis structures for these substances are ... 

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. 

In this chapter, you have learned about intermolecular forces, the forces between atoms, molecules, and/or ions. The types of intermolecular forces include ion-dipole forces, hydrogen bonding, ion-induced and dipole-induced forces, and London (dispersion) forces. 

In which of the following are London dispersion forces the most important intermolecular force present ... 

London (dispersion) forces are intermolecular forces between nonpolar molecules. 

Distinguish between dipole-dipole attraction forces and dispersion (London) forces. Is one type of these intermolecular forces stronger than the other Explain. 

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