Intermolecular forces chemical

Stone, A. J., Tough, R. J. A. (1984). Spherical tensor theory of long-range intermolecular forces. Chemical Physics Letters, 110,123-129. 

Substitution of fluorine for hydrogen in an organic compound has a profound influence on the compound s chemical and physical properties. Several factors that are characteristic of fluorine and that underHe the observed effects are the large electronegativity of fluorine, its small size, the low degree of polarizabiHty of the carbon—fluorine bond and the weak intermolecular forces. These effects are illustrated by the comparisons of properties of fluorocarbons to chlorocarbons and hydrocarbons in Tables 1 and 2. 

Many of these features are interrelated. Finely divided soHds such as talc [14807-96-6] are excellent barriers to mechanical interlocking and interdiffusion. They also reduce the area of contact over which short-range intermolecular forces can interact. Because compatibiUty of different polymers is the exception rather than the rule, preformed sheets of a different polymer usually prevent interdiffusion and are an effective way of controlling adhesion, provided no new strong interfacial interactions are thereby introduced. Surface tension and thermodynamic work of adhesion are interrelated, as shown in equations 1, 2, and 3, and are a direct consequence of the intermolecular forces that also control adsorption and chemical reactivity. 

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. 

The degree of polarity has considerable influence on the physical properties of covalent compounds and it can also affect chemical reactivity. The melting point (mp) and boiling point (bp) are higher in ionic substances due to the strong nature of the interionic forces, whereas the covalent compounds have lower values due to the weak nature of intermolecular forces. 

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 to refine our atomic and molecular model of matter to see how bulk properties can be interpreted in terms of the properties of individual molecules, such as their size, shape, and polarity. We begin by exploring intermolecular forces, the forces between molecules, as distinct from the forces responsible for the formation of chemical bonds between atoms. Then we consider how intermolecular forces determine the physical properties of liquids and the structures and physical properties of solids. 

Intermolecular forces are responsible for the existence of several different phases of matter. A phase is a form of matter that is uniform throughout in both chemical composition and physical state. The phases of matter include the three common physical states, solid, liquid, and gas (or vapor), introduced in Section A. Many substances have more than one solid phase, with different arrangements of their atoms or molecules. For instance, carbon has several solid phases one is the hard, brilliantly transparent diamond we value and treasure and another is the soft, slippery, black graphite we use in common pencil lead. A condensed phase means simply a solid or liquid phase. The temperature at which a gas condenses to a liquid or a solid depends on the strength of the attractive forces between its molecules. 

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. 

Network solids such as diamond, graphite, or silica cannot dissolve without breaking covalent chemical bonds. Because intermolecular forces of attraction are always much weaker than covalent bonds, solvent-solute interactions are never strong enough to offset the energy cost of breaking bonds. Covalent solids are insoluble in all solvents. Although they may react with specific liquids or vapors, covalent solids will not dissolve in solvents. 

Pectins are longchain macromolecules. In aqueous solutions they form more or less stiff rods or coils, depending on their degree of branching and linking as well as their molecular weight. In addition interparticular or intermolecular physical-chemical interactions like Van-der-Waals forces, ionic interactions or hydrogen bonds influence the active volume of the molecule, the stiffness and the viscosity. 

These models are semiempirical and are based on the concept that intermolecular forces will cause nonrandom arrangement of molecules in the mixture. The models account for the arrangement of molecules of different sizes and the preferred orientation of molecules. In each case, the models are fitted to experimental binary vapor-liquid equilibrium data. This gives binary interaction parameters that can be used to predict multicomponent vapor-liquid equilibrium. In the case of the UNIQUAC equation, if experimentally determined vapor-liquid equilibrium data are not available, the Universal Quasi-chemical Functional Group Activity Coefficients (UNIFAC) method can be used to estimate UNIQUAC parameters from the molecular structures of the components in the mixture3. 

The nature of intermolecular force is essentially no different from that which participates in the chemical bond or chemical reaction. The factor which determines the stable shape of a molecule, the influence on the reaction of an atom or group which does not take any direct part in the reaction, and various other sterically controlling factors might also be comprehended by a consideration based on the same theoretical foundation. 

Intermolecular forces exist between the atoms of molecules as a result of the interactions between the nuclei of one of the atoms and the electrons of the other. Although this sounds very similar to a general description of chemical bonding, there are a number of differences. Chemical bonds are permanent. In this case, permanent does not mean that they cannot react instead, it means that the atoms will remain bonded if they are not disturbed. Intermolecular forces do not share this permanency. The interactions occur very quickly and then, just as quickly, cease when translational and rotational motions separate the interacting species. 

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