Intermolecular forces phase

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. 

From the standpoint of thermodynamics, the dissolving process is the estabHsh-ment of an equilibrium between the phase of the solute and its saturated aqueous solution. Aqueous solubility is almost exclusively dependent on the intermolecular forces that exist between the solute molecules and the water molecules. The solute-solute, solute-water, and water-water adhesive interactions determine the amount of compound dissolving in water. Additional solute-solute interactions are associated with the lattice energy in the crystalline state. 

It follows from this discussion that all of the transport properties can be derived in principle from the simple kinetic dreoty of gases, and their interrelationship tlu ough k and c leads one to expect that they are all characterized by a relatively small temperature coefficient. The simple theory suggests tlrat this should be a dependence on 7 /, but because of intermolecular forces, the experimental results usually indicate a larger temperature dependence even up to for the case of molecular inter-diffusion. The Anhenius equation which would involve an enthalpy of activation does not apply because no activated state is involved in the transport processes. If, however, the temperature dependence of these processes is fitted to such an expression as an algebraic approximation, tlren an activation enthalpy of a few kilojoules is observed. It will thus be found that when tire kinetics of a gas-solid or liquid reaction depends upon the transport properties of the gas phase, the apparent activation entlralpy will be a few kilojoules only (less than 50 kJ). 

The distribution coefficient is an equilibrium constant and, therefore, is subject to the usual thermodynamic treatment of equilibrium systems. By expressing the distribution coefficient in terms of the standard free energy of solute exchange between the phases, the nature of the distribution can be understood and the influence of temperature on the coefficient revealed. However, the distribution of a solute between two phases can also be considered at the molecular level. It is clear that if a solute is distributed more extensively in one phase than the other, then the interactive forces that occur between the solute molecules and the molecules of that phase will be greater than the complementary forces between the solute molecules and those of the other phase. Thus, distribution can be considered to be as a result of differential molecular forces and the magnitude and nature of those intermolecular forces will determine the magnitude of the respective distribution coefficients. Both these explanations of solute distribution will be considered in this chapter, but the classical thermodynamic explanation of distribution will be treated first. 

We should point out that the calculations involved in Example 12.6 assume ideal gas behavior. At the conditions specified (1 atm, relatively high temperatures), this assumption is a good one. However, many industrial gas-phase reactions are carried out at very high pressures. In that case, intermolecular forces become important, and calculated yields based on ideal gas behavior may be seriously in error. 

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 liquid phase of matter is the most difficult to visualize. We have seen that a gas-phase molecule moves with almost complete freedom. The intermolecular forces from other molecules are minimal, and movement is highly disordered. In the solid phase, a molecule is locked in place by intermolecular forces and can only oscillate around an average location. The liquid phase lies between the extremes of the gas and solid phases. The molecules are mobile, blit they cannot escape from one another completely. 

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. 

Fig. 15. The low-frequency vibrational mode spectrum for 8CB in its smectic phase. The broad and weak spectral feature at about 8 cm has been attributed to intermolecular forces extending across smectic layers...

A 7/vap always is 3.10 kJ/mol greater than A fi vap At 298 K (25 °C, room temperature) A /Tvap always is 2.48 kJ/mol greater than A ivap The difference between A vap and A i7vap arises because, in addition to overcoming intermolecular forces in the condensed phase (A E), the escaping vapor must do work, w = A(P V ) — RT as it expands against the constant external pressure of the atmosphere. 

Forces of attraction between molecules are responsible for the existence of liquids and solids. In the absence of these intermolecular forces, all molecules would move independently, and all substances would be gases. The natural phases of the elements indicate the importance of intermolecular forces. At room temperature and pressure, only 11 elements are gases. Mercuiy and bromine are liquids, and all the rest of the elements are solids. For all but the 11 gaseous elements, intermolecular forces are too large to ignore under normal conditions. 

Gases and condensed phases look very different at the molecular level. Molecules of F2 or CI2 move freely throughout their gaseous volume, traveling many molecular diameters before colliding with one another or with the walls of their container. Because much of the volume of a gas is empty space, samples of gaseous F2 and CI2 readily expand or contract in response to changes in pressure. This freedom of motion exists because the intermolecular forces between these molecules are small. 

A substance exists in a condensed phase when its molecules have too little average kinetic energy to overcome intermolecular forces of attraction. 

The balance of average kinetic energy (red line and intermolecular forces of attraction favors the gas phase... 

A gas condenses to a liquid if it is cooled sufficiently. Condensation occurs when the average kinetic energy of motion of molecules falls below the value needed for the molecules to move about independently. Thus, the molecules in a liquid are confined to a specific volume by intermolecular forces of attraction. Although they cannot readily escape, liquid molecules remain free to move about within the liquid phase, hi this behavior, liquid molecules behave like the molecules of a gas. The large-scale consequences of the molecular-level properties are apparent. Like gases, liquids are fluid, so they flow easily from place to place. Unlike gases, however, liquids are compact, so they cannot expand or contract significantly. 

Figure 11-17 illustrates at the molecular level why liquids exhibit surface tension. A molecule In the Interior of a liquid is completely surrounded by other molecules. A molecule at a liquid surface, on the other hand, has other molecules beside It and beneath it but very few above it in the gas phase. This difference means that there is a net intermolecular force on molecules at the surface that pulls them toward the Interior of the liquid. 

When molecular energies are nearly sufficient to overcome intermolecular forces, molecules of a substance move relatively freely between the liquid phase and the vapor phase. We describe these phase changes in Section 11-1. 

Phase changes are characteristic of all substances. The normal phases displayed by the halogens appear in Section II-L where we also show that a gas liquefies or a liquid freezes at low enough temperatures. Vapor pressure, which results from molecules escaping from a condensed phase into the gas phase, is one of the liquid properties described in Section II-I. Phase changes depends on temperature, pressure, and the magnitudes of intermolecular forces. 

Energy must also be provided to melt a solid substance. This energy is used to overcome the intermolecular forces that hold molecules or ions in fixed positions in the solid phase. Thus, the melting of a solid also has characteristic energy and enthalpy changes. The heat needed to melt one mole of a substance at its normal melting point is called the molar heat of fusion, Ai/fas... 

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