Covalent molecules intermolecular forces

This arrangement of atoms produces a very polar bond, often resulting in a polar molecule with strong intermolecular attractive forces. Although the hydrogen bond is weaker than bonds formed within molecules (covalent and polar covalent intramolecular forces), it is the strongest attractive force between molecules (intermolecular force). 

Figure 9.13 Strong forces within molecules and weak forces between them. When pentane boils, weak forces between molecules (intermolecular forces) are overcome, but the strong covalent bonds holding the atoms together within each molecule remain unaffected. Thus, the pentane...

The van der Waals radius determines the shortest distance over which intermolecu-iar forces operate it is aiways larger than the covalent radius. Intermolecular forces are much weaker than bonding (intramolecular) forces. Ion-dipole forces occur between ions and poiar molecules. Dipole-dipole forces occur between oppositely charged poles on polar molecules. Hydrogen bonding, a special type of dipole-dipole force, occurs when H bonded to N, O, or F is attracted to the lone pair of N, O, or F in another molecule. Electron clouds can be distorted (polarized) in an electric field. Dispersion (London) forces are instantaneous dipole-induced dipole forces that occur among all particles and increase with number of electrons (molar mass). Molecular shape determines the extent of contact between molecules and can be a factor in the strength of dispersion forces. 

Notice that molecules are held together by bonds, sometimes called intramolecular forces, that occur inside the molecules. Intermolecular forces exist between molecules. We have seen that covalent bonding forces within molecules arise from the sharing of electrons, but how do intermolecular forces arise Actually several types of intermolecular forces exist. To illustrate one type, we will consider the forces that exist among water molecules. 

The generally low melting and boiling points of molecular substances reflect the fact that the forces between molecules (intermolecular forces) are weak. To melt or boil a molecular substance, the molecules must be set free from one another. This requires only that enough energy be supplied to overcome the weak attractive forces between molecules. The strong covalent bonds within molecules remain intact when a molecular substance melts or boils. 

In most covalent compounds, the strong covalent bonds link the atoms together into molecules, but the molecules themselves are held together by much weaker forces, hence the low melting points of molecular crystals and their inability to conduct electricity. These weak intermolecular forces are called van der WaaFs forces in general, they increase with increase in size of the molecule. Only... 

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. 

If the concentration of junction points is high enough, even branches will contain branches. Eventually a point is reached at which the amount of branching is so extensive that the polymer molecule becomes a giant three-dimensional network. When this condition is achieved, the molecule is said to be cross-linked. In this case, an entire macroscopic object may be considered to consist of essentially one molecule. The forces which give cohesiveness to such a body are covalent bonds, not intermolecular forces. Accordingly, the mechanical behavior of cross-linked bodies is much different from those without cross-linking. 

A useful property of liquids is their ability to dissolve gases, other liquids and solids. The solutions produced may be end-products, e.g. carbonated drinks, paints, disinfectants or the process itself may serve a useful function, e.g. pickling of metals, removal of pollutant gas from air by absorption (Chapter 17), leaching of a constituent from bulk solid. Clearly a solution s properties can differ significantly from the individual constituents. Solvents are covalent compounds in which molecules are much closer together than in a gas and the intermolecular forces are therefore relatively strong. When the molecules of a covalent solute are physically and chemically similar to those of a liquid solvent the intermolecular forces of each are the same and the solute and solvent will usually mix readily with each other. The quantity of solute in solvent is often expressed as a concentration, e.g. in grams/litre. 

When thinking about chemical reactivity, chemists usually focus their attention on bonds, the covalent interactions between atoms within individual molecules. Also important, hotvever, particularly in large biomolecules like proteins and nucleic acids, are a variety of interactions between molecules that strongly affect molecular properties. Collectively called either intermolecular forces, van der Waals forces, or noncovalent interactions, they are of several different types dipole-dipole forces, dispersion forces, and hydrogen bonds. 

We have now discussed three types of intermolecular forces dispersion forces, dipole forces, and hydrogen bonds. You should bear in mind that all these forces are relatively weak compared with ordinary covalent bonds. Consider, for example, the situation in HzO. The total intermolecular attractive energy in ice is about 50 kj/mol. In contrast, to dissociate one mole of water vapor into atoms requires the absorption of928 kj of energy, that is, 2(OH bond energy). This explains why it is a lot easier to boil water than to decompose it into the elements. Even at a temperature of 1000°C and 1 atm, only about one H20 molecule in a billion decomposes to hydrogen and oxygen atoms. 

The halogens, the elements from Group 17 of the periodic table, provide an introduction to intermolecular forces. These elements exist as diatomic molecules F2, CI2, Bf2, and I2. The bonding patterns of the four halogens are identical. Each molecule contains two atoms held together by a single covalent bond that can be described by end-on overlap of valence p orbitals. 

The term molecular crystal refers to crystals consisting of neutral atomic particles. Thus they include the rare gases He, Ne, Ar, Kr, Xe, and Rn. However, most of them consist of molecules with up to about 100 atoms bound internally by covalent bonds. The dipole interactions that bond them is discussed briefly in Chapter 3, and at length in books such as Parsegian (2006). This book also discusses the Lifshitz-Casimir effect which causes macroscopic solids to attract one another weakly as a result of fluctuating atomic dipoles. Since dipole-dipole forces are almost always positive (unlike monopole forces) they add up to create measurable attractions between macroscopic bodies. However, they decrease rapidly as any two molecules are separated. A detailed history of intermolecular forces is given by Rowlinson (2002). 

Intermolecular forces exist between covalent molecules in the solid and liquid states. There are two categories ... 

Intermolecular forces occur between molecules not within molecules. For example, covalent bonds hold a water molecule together, but intermolecular forces, not covalent bonds, attract separate water molecules to each other. 

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. 

To do this we assign an energy of interaction vvn to a pair of solvent molecules and w22 to a pair of polymer segments. The latter arises from the intermolecular forces between segments and not from the covalent bonds between them. In the same fashion, we define wl2 to be the energy of the solvent-segment interaction. 

The intermolecular forces of adhesion and cohesion can be loosely classified into three categories quantum mechanical forces, pure electrostatic forces, and polarization forces. Quantum mechanical forces give rise both to covalent bonding and to the exchange interactions that balance tile attractive forces when matter is compressed to the point where outer electron orbits interpenetrate. Pure electrostatic interactions include Coulomb forces between charged ions, permanent dipoles, and quadrupoles. Polarization forces arise from the dipole moments induced in atoms and molecules by the electric fields of nearby charges and other permanent and induced dipoles. 

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