Van-der-Waals compression

Finally, chemical-shift variations originating in van der Waals compression are noteworthy, although very few reports have come to our attention discussing signal shifts of sp3 carbon atoms in terms of van der Waals interactions. Schill and co-workers (89) found downfield shifts of up to 1 ppm in the [2]-catenane 5 when its 13C resonances are compared with those of the two isolated subunits. From the increase of these chemical-shift differences with increasing distance from the nitrogen atom, these authors concluded that the strongest van der Waals interactions occur in that part of the heterocycle which is opposite to the amide moiety in space (cf. Scheme 4). 

The mechanisms of substituent effects are numerous23 the most prominent being inductive, mesomeric, neighbor anisotropy, ring-current, electric-field and steric effects, as well as van der Waals compression. 

On compression, a gaseous phase may condense to a liquid-expanded, L phase via a first-order transition. This transition is difficult to study experimentally because of the small film pressures involved and the need to avoid any impurities [76,193]. There is ample evidence that the transition is clearly first-order there are discontinuities in v-a plots, a latent heat of vaporization associated with the transition and two coexisting phases can be seen. Also, fluctuations in the surface potential [194] in the two phase region indicate two-phase coexistence. The general situation is reminiscent of three-dimensional vapor-liquid condensation and can be treated by the two-dimensional van der Waals equation (Eq. Ill-104) [195] or statistical mechanical models [191]. 

Table 5.27 Compressibility of Water Table 5.28 Mass of Water Vapor In Saturated Air Table 5.29 Van der Waals Constants for Gases Table 5.30 Triple Points of Various M aterlals 5.9.1 Some Physical Chemistry Equations for Gases...

It can be seen from these two factors, ie, particle charge and van der Waals forces, that the charge must be reduced or the double layer must be compressed to aUow the particles to approach each other closely enough so that the van der Waals forces can hold them together. There are two approaches to the accomplishment of this goal reaction of the charged surface sites with an opposite charge on an insoluble material and neutralization of... 

Liquid crystals stabilize in several ways. The lamellar stmcture leads to a strong reduction of the van der Waals forces during the coalescence step. The mathematical treatment of this problem is fairly complex (28). A diagram of the van der Waals potential (Fig. 15) illustrates the phenomenon (29). Without the Hquid crystalline phase, coalescence takes place over a thin Hquid film in a distance range, where the slope of the van der Waals potential is steep, ie, there is a large van der Waals force. With the Hquid crystal present, coalescence takes place over a thick film and the slope of the van der Waals potential is small. In addition, the Hquid crystal is highly viscous, and two droplets separated by a viscous film of Hquid crystal with only a small compressive force exhibit stabiHty against coalescence. Finally, the network of Hquid crystalline leaflets (30) hinders the free mobiHty of the emulsion droplets. 

Since non-ideal gases do not obey the ideal gas law (i.e., PV = nRT), corrections for nonideality must be made using an equation of state such as the Van der Waals or Redlich-Kwong equations. This process involves complex analytical expressions. Another method for a nonideal gas situation is the use of the compressibility factor Z, where Z equals PV/nRT. Of the analytical methods available for calculation of Z, the most compact one is obtained from the Redlich-Kwong equation of state. The working equations are listed below ... 

Thus, from an investigation of the compressibility of a gas we can deduce the values of its critical constants. We observe that, according to van der Waals theory, liquid and gas are really two distant states on the same isotherm, and having therefore the same characteristic equation. Another theory supposes that each state has its own characteristic equation, with definite constants, which however vary with the temperature, so that both equations continuously coalesce at the critical point. The correlation of the liquid and gaseous states effected by van der Waals theory is, however, rightly regarded as one of the greatest achievements of molecular theory. 

Equations of state that are cubic in volume are often employed, since they, at least qualitatively, reproduce the dependence of the compressibility factor on p and T. Four commonly used cubic equations of state are the van der Waals, Redlich-Kwong, Soave, and Peng-Robinson. All four can be expressed in a reduced form that eliminates the constants a and b. However, the reduced equations for the last two still include the acentric factor u> that is specific for the substance. In writing the reduced equations, coefficients can be combined to simplify the expression. For example, the reduced form of the Redlich-Kwong equation is... 

Methods have been given for the calculation of the pressure drop for the flow of an incompressible fluid and for a compressible fluid which behaves as an ideal gas. If the fluid is compressible and deviations from the ideal gas law are appreciable, one of the approximate equations of state, such as van der Waals equation, may be used in place of the law PV = nRT to give the relation between temperature, pressure, and volume. Alternatively, if the enthalpy of the gas is known over a range of temperature and pressure, the energy balance, equation 2.56, which involves a term representing the change in the enthalpy, may be employed ... 

FIG. 2 Interaction forces between glass surfaces upon compression in ethanol-cyclohexane mixtures. The dashed and solid lines represent the van der Waals force calculated using the nonretarded Hamarker constants of 3 X 10 1 for glass/cyclohexane/glass and 6 X 10 J for glass/ethanol glass, respectively. 

Gases such as methane are sold and shipped in compressed gas cylinders. A typical cylinder has a volume of 15.0 L and, when full, contains 62.0 mol of CH4. After prolonged use, 0.620 mol of CH4 remains in the cylinder. Use the van der Waals equation to calculate the pressures in the cylinder when full and after use, and compare the values to those obtained from the ideal gas equation. Assume a temperature of 27 °C. 

At a finite distance, where the surface does not come into molecular contact, equilibrium is reached between electrodynamic attractive and electrostatic repulsive forces (secondary minimum). At smaller distance there is a net energy barrier. Once overcome, the combination of strong short-range electrostatic repulsive forces and van der Waals attractive forces leads to a deep primary minimum. Both the height of the barrier and secondary minimum depend on the ionic strength and electrostatic charges. The energy barrier is decreased in the presence of electrolytes (monovalent < divalent [Pg.355]

Parameters Bi , ai - and Ci - for light atoms have been listed by Gavezzoti [63], Examples of the resulting potential functions are shown in Fig. 5.1. The minimum point in each graph corresponds to the interatomic equilibrium distance between two single atoms. In a crystal shorter distances result because a molecule contains several atoms and thus several attractive atom-atom forces are active between two molecules, and because attractive forces with further surrounding molecules cause an additional compression. All attractive forces taken together are called van der Waals forces. 

Figure 5.2 (a) Electron density contour map of the CI2 molecule (see Chapter 6) showing that the chlorine atoms in a CI2 molecule are not portions of spheres rather, the atoms are slightly flattened at the ends of the molecule. So the molecule has two van der Waals radii a smaller van der Waals radius, r2 = 190 pm, in the direction of the bond axis and a larger radius, r =215 pm, in the perpendicular direction, (b) Portion of the crystal structure of solid chlorine showing the packing of CI2 molecules in the (100) plane. In the solid the two contact distances ry + ry and ry + r2 have the values 342 pm and 328 pm, so the two radii are r 1 = 171 pm and r2 = 157, pm which are appreciably smaller than the radii for the free CI2 molecule showing that the molecule is compressed by the intermolecular forces in the solid state. 

Chapter 6. The outer contour in this map is for a density of 0.001 au, which has been found to represent fairly well the outer surface of a free molecule in the gas phase, giving a value of 190 pm for the radius in the direction opposite the bond and 215 pm in the perpendicular direction. In the solid state molecules are squashed together by intermolecular forces giving smaller van der Waals radii. Figure 5.2b shows a diagram of the packing of the Cl2 molecules in one layer of the solid state structure of chlorine. From the intermolecular distances in the direction opposite the bond direction and perpendicular to this direction we can derive values of 157 pm and 171 pm for the two radii of a chlorine atom in the CI2 molecule in the solid state. These values are much smaller than the values for the free molecule in the gas phase. Clearly the Cl2 molecule is substantially compressed in the solid state. This example show clearly that the van der Waals of an atom radius is not a well defined concept because, as we have stated, atoms in molecules are not spherical and are also compressible. 

The constancy of the ligand radii, in contrast to van der Waals radii, suggests that gem-inal ligands on molecules of period 2 elements are squeezed together almost to their limit of compressibility. The repulsive interaction between two atoms is usually represented by a steeply rising potential such as that shown in Figure 5.7. This potential is often approximately represented by a function of the type... 

Two repulsive contributions, osmotic and elastic contributions [31, 32], oppose the van der Waals attractive contribution where the osmotic potential depends on the free energy of the solvent-ligand interactions (due to the solvation of the ligand tails by the solvent) and the elastic potential results from the entropic loss due to the compression of ligand tails between two metal cores. These repulsive contributions depend largely on the ligand length, solvent parameters, nanopartide radius, and center-to-center distance ... 

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