Intermolecular forces types

Indicator variables with extended significance referring to intermolecular force types in receptor-oligopeptide interactions, are described in paragraph 2,5. ... 

The next point of interest has to do with the question of how deep the surface region or region of appreciably unbalanced forces is. This depends primarily on the range of intermolecular forces and, except where ions are involved, the principal force between molecules is of the so-called van der Waals type (see Section VI-1). This type of force decreases with about the seventh power of the intermolecular distance and, consequently, it is only the first shell or two of nearest neighbors whose interaction with a given molecule is of importance. In other words, a molecule experiences essentially symmetrical forces once it is a few molecular diameters away from the surface, and the thickness of the surface region is of this order of magnitude (see Ref. 23, for example). (Certain aspects of this conclusion need modification and are discussed in Sections X-6C and XVII-5.)... 

As also noted in the preceding chapter, it is customary to divide adsorption into two broad classes, namely, physical adsorption and chemisorption. Physical adsorption equilibrium is very rapid in attainment (except when limited by mass transport rates in the gas phase or within a porous adsorbent) and is reversible, the adsorbate being removable without change by lowering the pressure (there may be hysteresis in the case of a porous solid). It is supposed that this type of adsorption occurs as a result of the same type of relatively nonspecific intermolecular forces that are responsible for the condensation of a vapor to a liquid, and in physical adsorption the heat of adsorption should be in the range of heats of condensation. Physical adsorption is usually important only for gases below their critical temperature, that is, for vapors. 

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. 

Dispersive Interactions. For pairs of nonpolar polymers, the intermolecular forces are primarily of the dispersive type, and in such cases the energy of interaction between unlike segments is expected to be closely approximated by the geometric mean of the energies of interaction between the two like pairs (98). In this case, the Flory-Huggins interaction energy between this polymer pair can be expressed in terms of the solubiUty parameters 5 of the pure components. 

Hydrophobic Interaction. This is the tendency of hydrophobic groups, especially alkyl chains such as those present in synthetic fibers, and disperse dyes to associate together and escape from the aqueous environment. Hydrophobic bonding is considered (7) to be a combination of van der Waals forces and hydrogen bonding taking place simultaneously rather than being a completely new type of bond or intermolecular force. 

Molecular interactions are the result of intermolecular forces which are all electrical in nature. It is possible that other forces may be present, such as gravitational and magnetic forces, but these are many orders of magnitude weaker than the electrical forces and play little or no part in solute retention. It must be emphasized that there are three, and only three, different basic types of intermolecular forces, dispersion forces, polar forces and ionic forces. All molecular interactions must be composites of these three basic molecular forces although, individually, they can vary widely in strength. In some instances, different terms have been introduced to describe one particular force which is based not on the type of force but on the strength of the force. Fundamentally, however, there are only three basic types of molecular force. 

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. 

Ihe boiling points of different molecular substances are directly related to the strength of the intermolecular forces involved. The stronger the intermolecular forces, the higher the boiling point of the substance. In the remainder of this section, we examine the nature of the three different types of intermolecular forces dispersion forces, dipole forces, and hydrogen bonds. 

The most common type of intermolecular force, found in all molecular substances, is referred to as a dispersion force. It is basically electrical in nature, involving an attraction between temporary or induced dipoles in adjacent molecules. To understand the origin of dispersion forces, consider Figure 9.8. 

What types of intermolecular forces are present in nitrogen, N2 Chloroform, CHCl3 Carbon dioxide, C02 Ammonia, NH3 ... 

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. 

Identify the type of intermolecular forces in different substances. 

We have seen that the pure elements may solidify in the form of molecular solids, network solids, or metals. Compounds also may condense to molecular solids, network solids, or metallic solids. In addition, there is a new effect that does not occur with the pure elements. In a pure element the ionization energies of all atoms are identical and electrons are shared equally. In compounds, where the most stable electron distribution need not involve equal sharing, electric dipoles may result. Since two bonded atoms may have different ionization energies, the electrons may spend more time near one of the positive nuclei than near the other. This charge separation may give rise to strong intermolecular forces of a type not found in the pure elements. 

Polyesters are another important class of polyols. There are many polyester types used, so a generic structure is shown in Scheme 4.4. They are often based on adipic acid and either ethylene glycol (ethylene adipates) or 1,4-butanediol (butylene adipates). Polyesters, because of the polar carbonyl groups, contribute more to intermolecular forces, and physical properties such as tear and impact resistance are often improved by using them. They are also utilized for their solvent and acid resistance and light stability. Relatively poor hydrolytic stability is... 

Real gases consist of atoms or molecules with intermolecular attractions and repulsions. Attractions have a longer range than repulsions. The compression factor is a measure of the strength and type of intermolecular forces. When Z > 1, intermolecular repulsions are dominant when Z < 2, attractions are dominant. 

Account for the following observations in terms of the type and strength of intermolecular forces, (a) The melting point of solid xenon is —112°C and that of solid argon is — 189°C. 

Self-Test 14.12A Water adheres to glass. Predict the type of intermolecular forces that form between glass and water. 

Cl l CH2CI 12CH2OCHv (a) Draw a Lewis structure for each molecule, name it, and classify it by functional group, (b) Which molecules are isomers of each other Are any chiral If so, which ones (c) For each molecule, list the types of intermolecular forces that are present, (d) Use your answers to parts (a) and (b) to predict the relative boiling points, from lowest to highest. 

The effect of molecular interactions on the distribution coefficient of a solute has already been mentioned in Chapter 1. Molecular interactions are the direct effect of intermolecular forces between the solute and solvent molecules and the nature of these molecular forces will now be discussed in some detail. There are basically four types of molecular forces that can control the distribution coefficient of a solute between two phases. They are chemical forces, ionic forces, polar forces and dispersive forces. Hydrogen bonding is another type of molecular force that has been proposed, but for simplicity in this discussion, hydrogen bonding will be considered as the result of very strong polar forces. These four types of molecular forces that can occur between the solute and the two phases are those that the analyst must modify by choice of the phase system to achieve the necessary separation. Consequently, each type of molecular force enjoins some discussion. 

You might learn about the structure of DNA at the end of your organic chemistry course. For right now, we will be focused on problems that deal primarily with small molecules and therefore, for our purposes, we should think of H-bonding as an interaction a type of intermolecular force. 

At the opposite extreme, molecular solids contain individual molecules bound together by various combinations of dispersion forces, dipole forces, and hydrogen bonds. Conforming to like dissolves like, molecular solids dissolve readily in solvents with similar types of intermolecular forces. Nonpolar I2, for instance, is soluble in nonpolar liquids such as carbon tetrachloride (CCI4). Many organic compounds are molecular solids that dissolve in organic liquids such as cyclohexane and acetone. 

The best solvent for a molecular solid Is one whose Intermolecular forces match the forces holding the molecules in the crystal. For a solid held together by dispersion forces, good solvents are nonpolar liquids such as carbon tetrachloride (CCI4) and cyclohexane (Cg H12) For polar solids, a polar solvent such as acetone works well. Example provides some practice in recognizing solubility types. 

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